Black ceramic additives, pigments, and formulations

ABSTRACT

Ceramic black materials for use as, or in, colorants, inks, pigments, dyes, additives and formulations utilizing these black materials. Black ceramics having silicon, oxygen and carbon, and methods of making these ceramics; formulations utilizing these black ceramics; and devices, structures and apparatus that have or utilize these formulations. Plastics, paints, inks, coatings, formulations, liquids and adhesives containing ceramic black materials, preferably polymer derived black ceramic materials, and in particular polysilocarb polymer derived ceramic materials.

This application is a divisional of Ser. No. 14/634,828 filed Feb. 28,2015, which: (i) claims under 35 U.S.C. §119(e)(1) the benefit of thefiling date of Feb. 28, 2014 of U.S. provisional application Ser. No.61/946,598; (ii) claims under 35 U.S.C. §119(e)(1) the benefit of thefiling date of Jan. 21, 2015 of U.S. provisional application Ser. No.62/106,094; (iii) is a continuation-in-part of U.S. patent applicationSer. No. 14/268,150 filed May 2, 2014, which claims, under 35 U.S.C.§119(e)(1), the benefit of the filing date of May 2, 2013 of U.S.provisional application Ser. No. 61/818,906 and the benefit of thefiling date of May 3, 2013 of U.S. provisional application Ser. No.61/818,981, the entire disclosures of each of which are incorporatedherein by reference.

BACKGROUND OF THE INVENTION Field of the Invention

The present inventions relate to black materials and formulationsutilizing these materials. Generally, the present inventions relate to:ceramic materials having blackness, black color, and which are black;starting compositions for these ceramic materials, and methods of makingthese ceramic materials; and formulations, compositions, materials anddevices that utilize or have these ceramic materials. In particular,embodiments of the present inventions include: black ceramics havingsilicon, oxygen and carbon, and methods of making these ceramics; anddevices, structures and apparatus that have or utilize theseformulations, plastics, paints, inks, coatings and adhesives containingthese black ceramics.

As used herein, unless stated otherwise, the terms “color,” “colors”“coloring” and similar such terms are be given their broadest possiblemeaning and would include, among other things, the appearance of theobject or material, the color imparted to an object or material by anadditive, methods of changing, modifying or affecting color, thereflected refracted and transmitted wavelength(s) of light detected orobserved from an object or material, the reflected refracted andtransmitted spectrum(s) of light detected or observed from an object ormaterial, all colors, e.g. white, grey, black, red, violet, amber,almond, orange, aquamarine, tan, forest green, etc., primary colors,secondary colors, and all variations between, and the characteristic oflight by which any two structure free fields of view of the same sizeand shape can be distinguish between.

As used herein, unless stated otherwise, the terms “black”, “blackness”,and similar such terms, are to be given there broadest possiblemeanings, and would include among other things, the appearance of anobject, color, or material: that is substantially the darkest colorowing to the absence, or essential absence of, or absorption, oressential abortion of light; where the reflected refracted andtransmitted spectrum(s) of light detected or observed from an object ormaterial has no, substantially no, and essentially no light in thevisible wavelengths; the colors that are considered generally black inany color space characterization scheme, including the colors that areconsidered generally black in L a b color space, the colors that areconsidered generally black in the Hunter color space, the colors thatare considered generally black in the CIE color space, and the colorsthat are considered generally black in the CIELAB color space; anycolor, or object or material, that matches or substantially matches anyPantone® color that is referred to as black, including PMS 433, Black 3,Black 4, Black 5, Black 6, Black 7, Black 2 2×, Black 3 2×, Black 4 2×,Black 5 2×, Black 6 2×, Black 7 2×, 412, 419, 426, and 423; values on aTri-stimulus Colorimeter of X=from about 0.05 to about 3.0; Y=from about0.05 to about 3.0, and Z=from about 0.05 to about 3.0; in non glossyformulations; a CIE L a b of L=less than about 40, less than about 20,less than about 10, less than about 1, and about zero, of “a”=of anyvalue; of “b”=of any value; and a CIE L a b of L=less than 50 and b=lessthan 1.0; an L value less than 30, a “b” value less than 0.5 (includingnegative values) and an “a” value less than 2 (including negativevalues); having a jetness value of about 200 M_(y) and greater, about250 M_(y) and greater, 300 M_(y) and greater, and greater; having anL=40 or less and a My of greater than about 250; having an L=40 or lessand a My of greater than about 300; having a dM value of 10; having a dMvalue of −15; and combinations and variations of these.

As used herein, unless stated otherwise, the term “gloss” is to be givenits broadest possible meaning, and would include the appearance fromspecular reflection. Generally the reflection at the specular angle isthe greatest amount of light reflected for any specific angle. Ingeneral, glossy surfaces appear darker and more chromatic, while mattesurfaces appear lighter and less chromatic.

As used herein, unless stated otherwise, the term “Jetness” is to begiven its broadest possible meaning, and would include among otherthings, a Color independent blackness value as measured by M_(y) (whichmay also be called the “blackness value”), or M_(c), the color dependantblackness value, and M_(y) and M_(c) values obtained from following DIN55979 (the entire disclosure of which is incorporated herein byreference).

As used herein, unless stated otherwise, the term “undertone,” “hue” andsimilar such terms are to be given their broadest possible meaning, andwould include among other things.

As used herein, unless stated otherwise, the terms “visual light,”“visual light source,” “visual spectrum” and similar such terms refersto light having a wavelength that is visible, e.g., perceptible, to thehuman eye, and includes light generally in the wave length of about 390nm to about 770 nm.

As used herein, unless stated otherwise, the term “paint” is to be givenits broadest possible meaning, and would include among other things, aliquid composition that after application as a thin layer to a substrateupon drying forms a thin film on that substrate, and includes all typesof paints such as oil, acrylic, latex, enamels, varnish, waterreducible, alkyds, epoxy, polyester-epoxy, acrylic-epoxy,polyamide-epoxy, urethane-modified alkyds, and acrylic-urethane.

As used herein, unless stated otherwise, the term “plastic” is to begiven its broadest possible meaning, and would include among otherthings, synthetic or semi-synthetic organic polymeric materials that arecapable of being molded or shaped, thermosetting, thermoforming,thermoplastic, orientable, biaxially orientable, polyolefins, polyamide,engineering plastics, textile adhesives coatings (TAC), plastic foams,styrenic alloys, acrylonitrile butadiene styrene (ABS), polyurethanes,polystyrenes, acrylics, polycarbonates (PC), epoxies, polyesters, nylon,polyethylene, high density polyethylene (HDPE), very low densitypolyethylene (VLDPE), low density polyethylene (LDPE), polypropylene(PP), polyvinyl chloride (PVC), polyethylene terephthalate (PET),polybutylene terephthalate (PBT), poly ether ethyl ketone (PEEK),polyether sulfone (PES), bis maleimide, and viscose (cellulose acetate).

As used herein, unless stated otherwise, the term “ink” is to be givenits broadest possible meaning, and would include among other things, acolored liquid for marking or writing, toner (solid, powder, liquid,etc.) for printers and copiers, and colored solids that are used formarking materials, pigment ink, dye ink, tattoo ink, pastes,water-based, oil-based, rubber-based, and acrylic-based.

As used herein, unless stated otherwise, the term “nail polish” andsimilar such terms, are to be given its broadest term, and would includeall types of materials, coatings and paints that can be applied to, orform a film, e.g., a thin film, on the surface of a nail, includingnatural human nails, synthetic “fake” nails, and animal nails.

As used herein, unless stated otherwise, the term “adhesive” is to begiven its broadest possible meaning, and would include among otherthings, substances (e.g., liquids, solids, plastics, etc.) that areapplied to the surface of materials to hold them together, a substancethat when applied to a surface of a material imparts tack or stickinessto that surface, and includes all types of adhesives, such as naturallyoccurring, synthetic, glues, cements, paste, mucilage, rigid,semi-rigid, flexible, epoxy, urethane, methacrylate, instant adhesives,super glue, permanent, removable, and expanding.

As used herein, unless stated otherwise, the term “coating” is to begiven its broadest possible meaning, and would include among otherthings, the act of applying a thin layer to a substrate, any materialthat is applied as a layer, film, or thin covering (partial or total) toa surface of a substrate, and includes inks, paints, and adhesives,powder coatings, foam coatings, liquid coatings, and includes the thinlayer that is formed on the substrate, e.g. a coating.

As used herein, unless stated otherwise, the term “sparkle” is to begiven its broadest possible meaning, and would include among otherthings, multi angle reflections simultaneously imparted from the surfacefacets.

As used herein, unless stated otherwise, room temperature is 25° C. And,standard temperature and pressure is 25° C. and 1 atmosphere.

Generally, the term “about” as used herein unless specified otherwise ismeant to encompass a variance or range of ±10%, the experimental orinstrument error associated with obtaining the stated value, andpreferably the larger of these.

SUMMARY

There has been a long-standing and unfulfilled need for, improvedpigments and additives for plastics, paints, inks, coatings andadhesives, as well as a continued need for improved formulations forthese coatings and materials. The present inventions, among otherthings, solve these needs by providing the compositions of matter,materials, articles of manufacture, devices and processes taught,disclosed and claimed herein.

There is provided a coating formulation having: a first material and asecond material; wherein the first material defines a first materialweight percent of the coating formulation and the second materialdefines a second material weight percent of the coating formulation;wherein the second material is a black polymer derived ceramic materialhaving from about 30 weight % to about 60 weight % silicon, from about 5weight % to about 40 weight % oxygen, and from about 3 weight % to about35 weight % carbon; and wherein the first material weight percent islarger than the second material weight percent.

There is further provided the pigments, coatings, coating formulationsand materials that have one or more of the following features: wherein20 weight % to 80 weight % of the carbon is free carbon; wherein 20weight % to 80 weight % of the carbon is silicon-bound-carbon; whereinthe formulation is selected from the group consisting of paint, powdercoat, adhesive, nail polish, and ink; wherein the black polymer derivedceramic material has a particle size of less than about 1.5 μm; whereinthe black polymer derived ceramic material has a particle size D₅₀ offrom about 1 μm to about 0.1 μm; wherein the coating defines a blacknessselected from the group consisting of: PMS 433, Black 3, Black 3, Black4, Black 5, Black 6, Black 7, Black 2 2×, Black 3 2×, Black 4 2×, Black5 2×, Black 6 2×, and Black 7 2×; wherein the coating defines ablackness selected from the group consisting of: Tri-stimulusColorimeter of X from about 0.05 to about 3.0, Y from about 0.05 toabout 3.0, and Z from about 0.05 to about 3.0; a CIE L a b of L of lessthan about 40; a CIE L a b of L of less about 20; a CIE L a b of L ofless than 50, b of less than 1.0 and a of less than 2; and a jetnessvalue of at least about 200 M_(y); wherein the formulation isessentially free of heavy metals; wherein the formulation has less thanabout 100 ppm of heavy metals; wherein the formulation has less thanabout 10 ppm heavy metals; wherein the formulation has less than about 1ppm heavy metals; wherein the formulation has less than about 0.1 ppmheavy metals; wherein the coating is essentially free of heavy metals;wherein the coating has less than about 100 ppm of heavy metals; whereinthe coating has less than about 10 ppm heavy metals; wherein the coatinghas less than about 1 ppm heavy metals; wherein the coating has lessthan about 0.1 ppm heavy metals; wherein the pigment has less than about10 ppm heavy metals, less than about 1 ppm heavy metals, and less thanabout 0.1 ppm heavy metals; and wherein the heavy metals are Cr and Mn.

Yet further there is provided a paint formulation having: a resin, asolvent, and a polymer derived ceramic pigment having from about 30weight % to about 60 weight % silicon, from about 5 weight % to about 40weight oxygen, and from about 3 weight % to about 35 weight % carbon,and wherein 20 weight % to 80 weight % of the carbon issilicon-bound-carbon.

There is further provided the pigments, coatings, coating formulationsand materials that have one or more of the following features:

wherein the polymer derived ceramic pigment has a primary particle D₅₀size of from about 0.1 μm to about 2.0 μm; wherein the polymer derivedceramic pigment is loaded at from about 1.5 pounds/gallon to about 10pounds/gallon; wherein the resin is selected from the group of resinsconsisting of thermoplastic acrylic polyols, Bisphenol A diglycidalether, silicone, oil based, and water-reducible acrylic; wherein theformulation has less than about 0.01 ppm of heavy metals; wherein theformulation has less than about 0.1 ppm of heavy metals; wherein theformulation has less than about 1 ppm of heavy metals, and the paintformulation is a very high temperature coating, wherein the paintformulation is thermally stable to greater than 700° C.; wherein theformulation has less than about 10 ppm of heavy metals, and the paintformulation is a very high temperature coating; wherein the paintformulation is a very high temperature coating, and wherein the paintformulation is thermally stable to greater than 1000° C.; wherein thefirst material has a system selected from the group of systemsconsisting of acrylics, lacquers, alkyds, latex, polyurethane,phenolics, epoxies and waterborne; wherein the first material has amaterial selected from the group consisting of HDPE, LDPE, PP, Acrylic,Epoxy, Linseed Oil, PU, PUR, EPDM, SBR, PVC, water based acrylicemulsions, ABS, SAN, SEBS, SBS, PVDF, PVDC, PMMA, PES, PET, NBR, PTFE,siloxanes, polyisoprene and natural rubbers; wherein the coatingformulation is a paint formulation selected from the group consisting ofoil, acrylic, latex, enamel, varnish, water reducible, alkyd, epoxy,polyester-epoxy, acrylic-epoxy, polyamide-epoxy, urethane-modifiedalkyd, and acrylic-urethane; and wherein the coating has a coatingselected from the group consisting of industrial coatings, residentialcoatings, furnace coatings, engine component coatings, pipe coatings,and oil field coatings.

Yet moreover there is provided an ink formulation having: a firstmaterial and a black polymer derived ceramic pigment having from about30 weight % to about 60 weight % silicon, from about 5 weight % to about40 weight % oxygen, and from about 3 weight % to about 35 weight %carbon, and wherein 20 weight % to 80 weight % of the carbon issilicon-bound-carbon.

Furthermore there is provided a nail polish formulation, having acarrier material and a black polymer derived ceramic pigment having fromabout 30 weight % to about 60 weight % silicon, from about 5 weight % toabout 40 weight % oxygen, and from about 3 weight % to about 35 weight %carbon, and wherein 20 weight % to 80 weight % of the carbon issilicon-bound-carbon.

Additionally there is provided a plastic material, having a firstmaterial and a second material, wherein the first material is a plasticand makes up at least 50% of the total weight of the plastic material,and the second material is a black polymer derived ceramic materialhaving from about 30 weight % to about 60 weight % silicon, from about 5weight % to about 40 weight % oxygen, and from about 3 weight % to about35 weight % carbon, and wherein 20 weight % to 80 weight % of the carbonis silicon-bound-carbon.

There is further provided the pigments, coatings, coating formulationsand materials that have one or more of the following features: whereinthe plastic is selected from the group consisting of HDPE, LDPE, PP,Acrylic, Epoxy, Linseed Oil, PU, PUR, EPDM, SBR, PVC, water basedacrylic emulsions, ABS, SAN, SEBS, SBS, PVDF, PVDC, PMMA, PES, PET, NBR,PTFE, siloxanes, polyisoprene and natural rubbers; wherein the plasticis selected from the group consisting of thermosetting, thermoforming,thermoplastic, orientable, biaxially orientable, polyolefins, polyamide,engineering plastics, textile adhesives coatings (TAC) and plasticfoams; wherein the plastic is selected from the group consisting ofstyrenic alloys, acrylonitrile butadiene styrene (ABS), polyurethanes,polystyrenes, acrylics, polycarbonates (PC), epoxies, polyesters, nylon,polyethylene, high density polyethylene (HDPE), very low densitypolyethylene (VLDPE); and wherein the plastic is selected from the groupconsisting of low density polyethylene (LDPE), polypropylene (PP),polyvinyl chloride (PVC), polyethylene terephthalate (PET), polybutyleneterephthalate (PBT), poly ether ethyl ketone (PEEK), polyether sulfone(PES), bis maleimide, and viscose (cellulose acetate).

Still additionally there is provided a paint having: a resin and apolymer derived ceramic pigment having from about 30 weight % to about60 weight % silicon, from about 5 weight % to about 40 weight % oxygen,and from about 3 weight % to about 35 weight % carbon, and wherein 20weight % to 80 weight % of the carbon is silicon-bound-carbon.

Yet further there is provided an ink having: a carrier material and ablack polymer derived ceramic pigment having from about 30 weight % toabout 60 weight % silicon, from about 5 weight % to about 40 weight %oxygen, and from about 3 weight % to about 35 weight % carbon, andwherein 20 weight % to 80 weight % of the carbon issilicon-bound-carbon.

Moreover there is provided a nail polish formulation having: a carriermaterial and a black polymer derived ceramic pigment having from about30 weight % to about 60 weight % silicon, from about 5 weight % to about40 weight % oxygen, and from about 3 weight % to about 35 weight %carbon, and wherein 20 weight % to 80 weight % of the carbon issilicon-bound-carbon.

Yet additionally there is provided an adhesive having: a carriermaterial and a black polymer derived ceramic pigment having from about30 weight % to about 60 weight % silicon, from about 5 weight % to about40 weight % oxygen, and from about 3 weight % to about 35 weight %carbon, and wherein 20 weight % to 80 weight % of the carbon issilicon-bound-carbon.

Further there is provided a coating having: a first material and asecond material; wherein the first material defines a first materialweight percent of the coating formulation and the second material has asecond material weight percent of the total coating formulation; andwherein the second material is a black polymer derived ceramic materialhaving from about 30 weight % to about 60 weight % silicon, from about 5weight % to about 40 weight % oxygen, and from about 3 weight % to about35 weight % carbon, and wherein 20 weight % to 80 weight % of the carbonis silicon-bound-carbon, and the first material weight percent is largerthan the second material weight percent.

There is further provided the pigments, coatings, coating formulationsand materials that have one or more of the following features: whereinthe coating is a paint; wherein the coating is a powder coat; whereinthe black polymer derived ceramic material has a particle size of lessthan about 1.5 μm; wherein the coating defines a blackness selected fromthe group consisting of: PMS 433, Black 3, Black 3, Black 4, Black 5,Black 6, Black 7, Black 2 2×, Black 3 2×, Black 4 2×, Black 5 2×, Black6 2×, and Black 7 2×; wherein the coating defines a blackness selectedfrom the group consisting of: Tri-stimulus Colorimeter of X from about0.05 to about 3.0, Y from about 0.05 to about 3.0, and Z from about 0.05to about 3.0; a CIE L a b of L of less than about 40; a CIE L a b of Lof less about 20; a CIE L a b of L of less than 50, b of less than 1.0and a of less than 2; and a jetness value of at least about 200 M_(y);and wherein the paint is a paint selected from the group consisting ofoil, acrylic, latex, enamel, varnish, water reducible, alkyd, epoxy,polyester-epoxy, acrylic-epoxy, polyamide-epoxy, urethane-modifiedalkyd, and acrylic-urethane; wherein the coating is essentially free ofheavy metals; wherein the coating has less than about 10 ppm of heavymetals.

Additionally there is provided a paint having a resin and a polymerderived pigment having from about 30 weight % to about 60 weight %silicon, from about 5 weight % to about 40 weight % oxygen, and fromabout 3 weight % to about 35 weight % carbon, and wherein 20 weight % to80 weight of the carbon is silicon-bound-carbon.

There is further provided the pigments, coatings, coating formulationsand materials that have one or more of the following features: whereinthe first material has a material selected from the group of materialsconsisting of acrylics, lacquers, alkyds, latex, polyurethane,phenolics, epoxies and waterborne; wherein the coating is a paintselected from the group consisting of oil, acrylic, latex, enamel,varnish, water reducible, alkyd, epoxy, polyester-epoxy, acrylic-epoxy,polyamide-epoxy, urethane-modified alkyd, and acrylic-urethane; whereinthe black polymer derived ceramic material has about 40 weight % toabout 50 weight % silicon, and wherein about 25 weight % to about 40weight % of the carbon is silicon-bound-carbon; wherein the blackpolymer derived ceramic material has about 40 weight % to about 50weight % silicon, and wherein about 55 weight % to about 75 weight % ofthe carbon is free carbon; wherein the black polymer derived ceramicmaterial has about 20 weight % to about 30 weight % oxygen, and whereinabout 25 weight % to about 40 weight % of the carbon issilicon-bound-carbon; wherein the black polymer derived ceramic materialhas about 20 weight % to about 30 weight % oxygen, and wherein about 55weight % to about 75 weight % of the carbon is free carbon; wherein theblack polymer derived ceramic material has about 20 weight % to about 30weight % carbon, and wherein about 25 weight % to about 40 weight % ofthe carbon is silicon-bound-carbon; wherein the black polymer derivedceramic material has about 20 weight % to about 30 weight % carbon, andwherein about 55 weight % to about 75 weight % of the carbon is freecarbon; wherein the black polymer derived ceramic material has about 40weight % to about 50 weight % silicon, and wherein about 25 weight % toabout 40 weight % of the carbon is silicon-bound-carbon; wherein theblack polymer derived ceramic material has about 40 weight % to about 50weight % silicon, and wherein about 55 weight % to about 75 weight % ofthe carbon is free carbon; wherein the black polymer derived ceramicmaterial has about 20 weight % to about 30 weight % oxygen, and whereinabout 25 weight % to about 40 weight % of the carbon issilicon-bound-carbon; wherein the black polymer derived ceramic materialhas about 20 weight % to about 30 weight % oxygen, and wherein about 55weight % to about 75 weight % of the carbon is free carbon; wherein theblack polymer derived ceramic material has about 20 weight % to about 30weight % carbon, and wherein about 25 weight % to about 40 weight % ofthe carbon is silicon-bound-carbon; and wherein the black polymerderived ceramic material has about 20 weight % to about 30 weight %carbon, and wherein about 55 weight % to about 75 weight % of the carbonis free carbon.

Furthermore there is provided a black polysilocarb derived ceramicpigment having from about 30 weight % to about 60 weight % silicon, fromabout 5 weight % to about 40 weight % oxygen, and from about 3 weight %to about 35 weight % carbon, and wherein 20 weight % to 80 weight % ofthe carbon is silicon-bound-carbon and 80 weight % to about 20 weight %of the carbon is free carbon.

There is further provided the pigments, coatings, coating formulationsand materials that have one or more of the following features: whereinthe pigment is a UV absorber; wherein the pigment has an absorptioncoefficient of greater than 500 dB/cm/(g/100 g); wherein the pigment hasan absorption coefficient of greater than 500 dB/cm/(g/100 g); whereinthe pigment has an absorption coefficient of greater than 1,000dB/cm/(g/100 g); wherein the pigment has an absorption coefficient ofgreater than 5,000 dB/cm/(g/100 g); wherein the pigment has anabsorption coefficient of greater than 10,000 dB/cm/(g/100 g); whereinthe pigment has an agglomerate of primary pigment particles; wherein theagglomerate has a size D₅₀ of at least about 10 μm; wherein the primarypigment particles have a size D₅₀ of less than about 1 μm; wherein theagglomerate has a strength A_(s) and the primary particle has a strengthPP_(s) and PP_(s) is at least 100 times greater than A_(s); wherein theagglomerate has a strength A_(s) and the primary particle has a strengthPP_(s) and PP_(s) is at least 500 times greater than A_(s); wherein theagglomerate has a strength A_(s) and the primary particle has a strengthPP_(s) and PP_(s) is at least 1,000 times greater than A_(s); whereinthe pigment has an oil absorption of less than about 50 g/100 g; whereinthe pigment has an oil absorption of less than about 20 g/100 g; whereinthe polymer derived ceramic pigment has a primary particle D₅₀ size offrom about 0.1 μm to about 1.5 μm; wherein the polymer derived ceramicpigment has a primary particle D₅₀ size of greater than about 0.1 μm;wherein the polymer derived ceramic pigment has a primary particle D₅₀size of less than about 10.0 μm; wherein the polymer derived ceramicpigment has a primary particle D₅₀ size of from about 0.1 μm to about3.0 μm; wherein the polymer derived ceramic pigment has a primaryparticle D₅₀ size of from about 1 μm to about 5.0 μm; wherein thepigment is microwave safe; wherein the pigment is non-conductive;wherein the pigment is hydrophilic; and wherein the pigment ishydrophobic.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic flow diagram of an embodiment of a system inaccordance with the present inventions.

FIG. 2A is a scanning electron photomicrograph (SEPM) of an embodimentof a polysilocarb derived ceramic pigment. SEPM legend bar—HV 5.00 kV,WD 10.6 mm, magnification 5,000×, dwell 5 μs, spot 5.0, HFW 41.4 μm.

FIG. 2B is a SEPM of an embodiment of a polysilocarb derived ceramicpigment. SEPM legend bar—HV 5.00 kV, WD 10.6 mm, magnification 10,000×,dwell 5 μs, spot 5.0, HFW 20.7 μm.

FIG. 3A is a SEPM of an embodiment of a polysilocarb derived ceramicpigment. SEPM legend bar—HV 5.00 kV, WD 10.5 mm, magnification 5,000×,dwell 5 μs, spot 5.0, HFW 41.4 μm.

FIG. 3B is a SEPM of an embodiment of a polysilocarb derived ceramicpigment. SEPM legend bar—HV 5.00 kV, WD 10.5 mm, magnification 10,000×,dwell 5 μs, spot 5.0, HFW 20.7 μm.

FIG. 4A is a SEPM of an embodiment of a polysilocarb derived ceramicpigment. SEPM legend bar—HV 5.00 kV, WD 10.8 mm, magnification 6,500×,dwell 5 μs, spot 5.0, HFW 31.9 μm.

FIG. 4B is a SEPM of an embodiment of a polysilocarb derived ceramicpigment. SEPM legend bar—HV 5.00 kV, WD 10.8 mm, magnification 8,000×,dwell 2 μs, spot 5.0, HFW 25.9 μm.

FIG. 4C is a SEPM of an embodiment of a polysilocarb derived ceramicpigment. SEPM legend bar—HV 5.00 kV, WD 10.8 mm, magnification 65,000×,dwell 5 μs, spot 5.0, HFW 31.9 μm.

FIG. 5A is a SEPM of an embodiment of a polysilocarb derived ceramicpigment. SEPM legend bar—HV 5.00 kV, WD 10.1 mm, magnification 6,500×,dwell 5 μs, spot 5.0, HFW 31.9 μm.

FIG. 5B is a SEPM of an embodiment of a polysilocarb derived ceramicpigment. SEPM legend bar—HV 5.00 kV, WD 10.6 mm, magnification 10,000×,dwell 5 μs, spot 5.0, HFW 20.7 μm.

FIG. 5C is a SEPM of an embodiment of a polysilocarb derived ceramicpigment. SEPM legend bar—HV 5.00 kV, WD 10.4 mm, magnification 20,000×,dwell 2 μs, spot 5.0, HFW 10.4 μm.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

In general the present inventions relate to ceramic black materials foruse as, or in, colorants, inks, pigments, dyes, additives andformulations utilizing these black materials. Embodiments of the presentinventions, among other things, relate to ceramic materials havingblackness, black color, and which are black; starting compositions forthese ceramic materials, and methods of making these ceramic materials;and formulations, compositions, materials that utilize or have theseceramic materials. These various embodiments of the present inventions,in particular, relate to, or utilize, such ceramic black materials thatare polymer derived ceramics. Embodiments of the present inventions alsorelate to black ceramics having silicon, oxygen and carbon, and methodsof making these ceramics; formulations utilizing these black ceramics;and devices, structures and apparatus that have or utilize theseformulations. Embodiments of the present invention in general includeplastics, paints, inks, coatings, formulations, liquids and adhesivescontaining ceramic black materials, preferably polymer derived blackceramic materials, and more preferably polysilocarb polymer derivedceramic materials.

Polymer derived ceramics (PDC) are ceramic materials that are derivedfrom, e.g., obtained by, the pyrolysis of polymeric materials. Thesematerials are typically in a solid or semi-solid state that is obtainedby curing an initial liquid polymeric precursor, e.g., PDC precursor,PDC precursor formulation, precursor batch, and precursor. The cured,but unpyrolized, polymer derived material can be referred to as apreform, a PDC preform, the cured material, and similar such terms.Polymer derived ceramics may be derived from many different kinds ofprecursor formulations, e.g., starting materials, starting formulations.PDCs may be made of, or derived from, carbosilane or polycarbosilane(Si—C), silane or polysilane (Si—Si), silazane or polysilazane(Si—N—Si), silicon carbide (SiC), carbosilazane or polycarbosilazane(Si—N—Si—C—Si), siloxane or polysiloxanes (Si—O), to name a few.

A preferred PDC is “polysilocarb”, e.g., material containing silicon(Si), oxygen (O) and carbon (C). Polysilocarb materials may also containother elements. Polysilocarb materials can be made from one or morepolysilocarb precursor formulation or precursor formulation. Thepolysilocarb precursor formulations can contain, for example, one ormore functionalized silicon polymers, other polymers, non-silicon basedcross linking agents, monomers, as well as, potentially otheringredients, such as for example, inhibitors, catalysts, initiators,modifiers, dopants, fillers, reinforcers and combinations and variationsof these and other materials and additives. Silicon oxycarbidematerials, SiOC compositions, and similar such terms, unlessspecifically stated otherwise, refer to polysilocarb materials, andwould include liquid materials, solid uncured materials, curedmaterials, and ceramic materials.

Examples of PDCs, PDC formulations and starting materials, are found inU.S. patent application Ser. Nos. 14/212,986, 14/268,150, 14/324,056,14/514,257, 61/946,598, and 62/055,397, US Patent Publication No2008/0095942, 2008/0093185, 2007/0292690, 2006/0230476, 2006/0069176,2006/0004169, and 2005/0276961, and U.S. Pat. Nos. 5,153,295, 4,657,991,7,714,092, 7,087,656 and 8,742,008, and 8,119,057, the entiredisclosures of each of which are incorporated herein by reference.

Turning to FIG. 1 there is provided a process flow chart 100 for anembodiment having several embodiments of the present processes andsystems. Thus, there is a precursor make-up segment 101, where the PDCprecursor formulations are prepared. There is a forming segment 102where the PDC precursor is formed into a shape, e.g., bead, slab, andparticle. There is a curing segment 103, where the PDC precursor iscured to a cured material, which is substantially solid, and preferablya solid. There is a pyrolysis segment 104 where the cured material isconverted to a ceramic, e.g., a PDC, which preferably is a SiOC. Thereis a post-processing segment 105, where the ceramic is furtherprocessed, e.g., washing, grinding, agglomeration, milling, cycloning,sieving, etc. There is a formulation segment 106 where the PDC isprocessed into a material formulation (e.g., paint, plastic, ink,coating and adhesive), containing the PDC, i.e., a PDC containingmaterial formulation. PDC containing material formulations include,among other things, PDC paints, PDC plastics, PDC inks, PDC adhesives,and PDC coatings. There is an application segment 107, where a PDCcontaining material formulation is applied to a substrate, e.g., arefrigerator, vehicle, appliance or other items, and components of suchitems.

The precursor make-up segment can be any of the systems, processes andmaterials disclosed and taught in this specification, as well as, thosedisclosed and taught in U.S. patent application Ser. Nos. 14/212,986,14/268,150, 14/324,056, 14/514,257, 61/946,598 and 62/055,397 and62/106,094, the entire disclosure of each of which are incorporatedherein by reference.

The forming segment can be any of the systems, processes and materialsdisclosed and taught in this specification, as well as, those disclosedand taught in U.S. patent application Ser. Nos. 14/212,986, 14/268,150,14/324,056, 14/514,257, 61/946,598 and 62/055,397 and 62/106,094, theentire disclosure of each of which are incorporated herein by reference.

The curing segment can be any of the systems, processes and materialsdisclosed and taught in this specification, as well as, those disclosedand taught in U.S. patent application Ser. Nos. 14/212,986, 14/268,150,14/324,056, 14/514,257, 61/946,598 and 62/055,397 and 62/106,094, theentire disclosure of each of which are incorporated herein by reference.

The pyrolizing segment can be any of the systems, processes andmaterials disclosed and taught in this specification, as well as, thosedisclosed and taught in U.S. patent application Ser. Nos. 14/212,986,14/268,150, 14/324,056, 14/514,257, 61/946,598 and 62/055,397 and62/106,094, the entire disclosure of each of which are incorporatedherein by reference. By way of example, furnaces can that can be usedfor the pyrolizing segment include, among others: RF furnaces, Microwavefurnaces, pressure furnaces, fluid bed furnaces, box furnaces, tubefurnaces, crystal-growth furnaces, arc melt furnaces, inductionfurnaces, kilns, MoSi₂ heating element furnaces, gas-fired furnaces,carbon furnaces, and vacuum furnaces.

The post-processing segment can involve any type of further processingactivities to enhance, effect, or modify the performance, handleability,processability, features, size, surface properties, and combinations andvariations of these. Thus, for example, the post-processing step caninvolve a grinding step in which the PDC is reduced in size to diametersof less than about 10 μm, less than about 5 μm, less than about 1 μm,less than about 0.5 μm, and less than about 0.1 μm. The PDC can beground, for example, by the use of a ball mill, an attrition mill, arotor stator mill, a hammer mill, a jet-mill, a roller mill, a beadmill, a media mill, a grinder, a homogenizer, a two-plate mill, a doughmixer, and other types of grinding, milling and processing apparatus.The post-processing segment can involve, for example, an agglomeration,where smaller PDC particles are combined to form larger particles,preferably agglomerated particles having diameters of at least about 2μm, at least about 2.5 μm, greater than 2.5 μm, at least about 3 μm, atleast about 5 μm, at least about 10 μm, greater than 10 μm, and greaterthan 12 μm. Preferably, the agglomerated particles are sufficientlybound, or held together, to prevent the particles from falling off,e.g., separating from, the agglomeration during handling, shipping,storage, and processing, e.g., “handling strength.” More preferably, thestrength of the agglomerations is only slightly greater than thehandling strength, and in this manner can readily be broken apart intothe smaller particles for use in a PDC material formulation. Forexample, the agglomeration can have a strength, e.g., crush strength,that is less than about 1/2000 of the strength of the smaller particles,e.g., primary particles, that form the agglomeration, less than about1/500 of the strength of the smaller particles, less than about 1/75 ofthe strength of the smaller particles, and less than ½ of the strengthof the smaller particles. The agglomeration can, for example, be formedby using spray drying techniques. Suitable binders, including forexample sizing agents, for use in spray drying techniques include forexample: dispersants, surfactants, soaps, copolymers, starches, naturaland synthetic polymers and saccharides, lipids, fatty acids,petroleum-derived polymers and oligomers. Sodium alginate, corn starch,potato starch, and other naturally derived starches, fructoses,sucroses, dextroses and other naturally or synthetically derivedsaccharides and sugars, polylactic acid and other naturally derivedpolymers, cellulosic byproducts, carrageenan and other natural products,poly vinyl acetate and other water-soluble polymers, wetting anddispersing agents such as polyacrylates, polyethylene oxides,polypropylene oxides, and copolymers containing them. Parrafins andother waxes, other petrochemical derivatives and petroleum basedpolymers. Surfactants such as Tween, Span, Brij, and other types ofsurfactants; Stearates, oleates, and other modified oils; linearcopolymers, branched copolymers, star polymers and copolymers,hyperbranched polymers and copolymers, comb-like polymers, andcombinations and variations of these.

The amount of binder used to PDC can range from about 0.01% to 5%, about0.1% to about 2%, and preferably less than about 1% and less than about0.5%. Agglomerates can also be formed by batch evaporation and casting,thin film evaporation, wiped-film evaporation, tray drying, oven drying,freeze drying, and other suitable evaporation methods, aggregationtechniques such as sedimentation, solvent exchange and coagulation, pinmixing, filtration, and others, preferably combined with a dryingtechnique, and combinations and variations of these. Further, processingmay involve the application of a surface treatment, wash, or coating tothe surface of the PDC particles to provide predetermined features tothe PDCs, such as for example, enhanced antistatic, wettability,material formulation compatibility, mixability, etc. It should be notedthat while surface treatments are contemplated by the present inventionsto further enhance, e.g., specialize the PDC particles for a particularpurpose; an advantage of the present inventions is the feature that theyare more readily mixed, added, or compiled into material formations,e.g., paints, plastics, inks, coating and adhesives, than the prior artblack pigments, e.g., carbon black ((ASTM Color Index) CI Black 1,6,7)or graphite (CI Black 10) or metal oxides and mixed metal oxides,including but not limited to iron oxides (CI Black 11) and ManganeseIron oxide (CI Black 26) or Iron Manganese oxide (CI Black 33),Manganese oxide (CI Black 14), Copper oxide (CI Black 13), CopperManganese Iron oxide (CI Black 26) or Copper Chrome oxide (CI Black 28),and pigment made by ashing organic matter (CI Black 8, 9) whichtypically for many applications require surface treatments. Thus, anadvantage of the present inventions, among other things, is the abilityto use untreated PDC particles, e.g., no surface treatments, inmaterials formulation.

In the formulation segment, the making of the PDC material formulationtakes place. Thus, for example, the PDC ceramic is mixed into, added to,or otherwise combined with the materials used to make up the materialformulation. Generally, an agglomerate easily breaks down into itsprimary particles, e.g., the primary party state; and the primaryparticles are uniformly and smoothly distributed or suspended in theprimary formulation material, which can be obtained in less than 60minutes of mixing, less than 30 minutes of mixing and quicker.Typically, the PDC ceramic is much more easily mixed into the materialformulation than carbon black to a fully dispersed state. For example,and by way of illustration, PDC ceramic can be easily and quickly mixedwithin 10 minutes into a vessel in which a simple 3 blade stirrer ismixing at 1,000 rpm tip speed. The resin, PDC Ceramic mixture will befully dispersed which is illustrated by a reading of greater than 7 onthe Hegman gauge. The Hegman gauge is a calibrated device to quicklyshow how fine a dispersion is made. A carbon black or oxide blackpigment mixed into the resin in the same manner would produce a Hegmanreading of less than 1 which indicates very large particles still in theresin, because these pigments require high energy milling to break upthe aggregates in the ‘as supplied’ pigment. Generally, the PDC ceramiccan be mixed into, added to, or otherwise combined with the materialformulation in the same manner, using the same or existing equipment,that are present for use with other black pigments or colorants.Preferably, for many applications less expensive, quicker, moreefficient equipment and much less expensive processes than are neededfor carbon black can be used with the PDC particles.

In the application segment the PDC containing material formulation isapplied to an end product, or a component that may be used in an endproduct. The PDC containing material formulation can typically, andpreferably, be applied using the same types of techniques that are usedfor carbon black based formulations, e.g., brush, spray, dip, etc.Moreover, the PDC containing material formulations have applications,and the ability to be applied, in manners that could not be accomplishedwith a similar carbon black based formulation.

It should be understood that the various segments of the embodiment ofFIG. 1 can be combined (e.g., a single piece of equipment could performone of more of the operations of different segments, such as curing andpyrolizing), conducted serially, conducted in parallel, conductedmultiple times, omitted (e.g., post-processing many not be necessary orrequired), conducted in a step wise or batch process (included where thesegments are at different locations, separated by time, e.g., a fewhours, a few days, months or longer, and both), conducted continuously,and in different orders and combinations and variations of these. Thus,for example the post-processing segment of grinding can be performed onthe cured material prior to pyrolysis, and can also be performed on boththe cured and pyrolized materials.

FIGS. 2A and 2B, are SEPMs of an embodiment of a polysilocarb derivedceramic pigment having a primary particle size of 3 μm D₅₀, that wasmade by curing and pyrolizing the polysilocarb precursor formulationinto a monolithic block, and then breaking down that block into primaryparticles. FIGS. 3A and 3B are SEPMs of agglomerates formed by spraydrying 0.5 μm D₅₀ primary particles, which were obtained by furthermilling of the 3.0 μm primary particles shown in FIGS. 2A and 2B.

FIGS. 4A, 4B and 4C, are SEPMs of 1.5 μm D₅₀ primary particles of anembodiment of a polysilocarb derived ceramic pigment, that were formedby a liquid-liquid system. (Liquid-liquid systems are described and setforth in detail in U.S. Patent Application Ser. No. 62/106,094, theentire disclosure of which is incorporated herein by reference) andgenerally involve the formation of a drop of precursor material inanother liquid, and would include for example solution polymerizationtype systems, emulsion polymerization type systems, nano-emulsionformation type systems, and the like.) FIGS. 5A and 5B are SEPMs of theprimary particles of FIGS. 4A and 4B that have been further milled downto 0.9 μm D₅₀.

An embodiment of a polysilocarb ceramic pigment is a colorant suitableand advantageous in multiple fields such as industrial, architectural,marine and automotive systems. The polysilocarb ceramic pigment canpreferably easily disperses into acrylics, lacquers, alkyds, latex,Polyurethane, phenolics, epoxies and waterborne systems providing adurable, uniform coating and pleasant aesthetics in all types offinishes, e.g., matte and gloss.

The polysilocarb ceramic pigment can preferably be low dusting. Thepolysilocarb ceramic pigment does not typically accumulate charge, it iseasy to clean up, and does not cling to surfaces. The polysilocarbceramic pigment is considerably easier to clean up, and control dustingthan typical carbon black. It is theorized that the typical carbonblack's strong hydrophobicity, light particle weight, and very smallparticle size (e.g., 50 nm to 200 nm), among other things, makes carbonblack much more difficult to clean up and control than the polysilocarbceramic pigment. As such, it is preferably a non-sticking, non-clingingblack pigment. These, among other features, are a significantimprovement over carbon black, which is typically difficult to clean up,dusts, and clings to surfaces.

The polysilocarb ceramic pigment can have low oil absorption, leading tolower viscosities, which among other things, permits formulations tomove to higher solids loading with lower VOC content. This pigment canhave a diameter, for example, from about 0.1 μm to 300 μm, from about 1μm to about 150 μm, less than 10 μm, less than 1 μm, less than 0.3 μm,and less than or equal to 0.1 μm.

An embodiment of a batch of the polysilocarb pigment, can have narrow ortight particle size (e.g., diameter) distribution. Thus, embodiments ofthese black ceramic pigments are particles that are within at least 90%of the targeted size, at least 95% of the targeted size, and at least99% of the targeted size. For example, the patch of particles, can havesize distributions such as at least about 90% of their size within a 10μm range, at least about 95% of their size within a 10 μm range, atleast about 98% of their size within a 10 μm range, and at least about99% of their size within a 10 μm range. Further, and for example, theprocess can produce particles each of which can have at least about 90%of their size within a 5 μm range, at least about 95% of their sizewithin a 5 μm range, at least about 98% of their size within a 5 μmrange, and at least about 99% of their size within a 5 μm range.Further, and in submicron particle sized, for example, the process canproduce particles each of which can have at least about 90% of theirsize within a 0.2 μm range, at least about 95% of their size within a0.2 μm range, at least about 98% of their size within a 0.2 μm range,and at least about 99% of their size within a 0.2 μm range. Morepreferably, in sub micron sizes, embodiments these percentage tolerancescan be for the 0.1 μm range, and the 0.05 μm range. Preferably, theselevels of uniformity in the production of the particles are obtainedwithout the need for filtering, sorting or screening the particles.

It should further be noted that preferably these size distributions arefor particles, as used in the formulation. Thus, these particle sizedistributions can be agglomerated, and then upon de-agglomeration andpreferably will have the same, substantially the same particle sizedistribution. In this manner, preferably the particle size, and sizedistribution after de-agglomeration are predictable and predetermined.

In a preferred embodiment the polysilocarb pigments is a blacknon-conductive, acid and alkali resistant, and thermally stable up toabout 300° C., up to about 400° C. and up to about 500° C., or greater.In other embodiments the conductive properties of the pigment can bemodified with additives and fillers, during the making of the pigment,and in this way providing a pigment that is conductive, and has apredetermined conductivity. The color and jetness of these blackpolysilocarb pigments is typically a function of the particle size. In apreferred embodiment of the polysilocarb pigment, mass-tone and tintstrength can be comparable to, and in a further preferred embodiment canbe superior to, current black pigments, e.g., carbon, carbonaceous, andoxide based black pigments. In preferred embodiments the polysilocarbpigments are non-hazardous, having no toxicological effects.

Embodiments of the black polysilocarb pigments can be used in, amongother things, spray, brush-on and power coatings for applications onessentially all metal, ceramic and plastic surfaces in the industrial,marine, architectural, graphic arts & inks, and automotive fields.Embodiments of these pigments further can find applications incosmetics, nail polish, food packaging, and pharmaceutical applicationsand fields, to name a few.

Embodiments of the black polymer derived ceramic pigments are easilydispersed in most media. The black polysilocarb pigments are easily andreadily dispersed in most types of media, basis, resins and carriers.For example, HDPE, LDPE, PP, Acrylic, Epoxy, Linseed Oil, PU, PUR, EPDM,SBR, PVC, water based acrylic emulsions, ABS, SAN, SEBS, SBS, PVDF,PVDC, PMMA, PES, PET, NBR, PTFE, siloxanes, polyisoprene and naturalrubbers, and combinations of these and others.

Embodiments of the black polymer derived ceramic pigments have very lowoil absorption. The oil absorption for polysilocarb ceramic pigments canbe less than about 50 (grams linseed oil per 100 grams of pigment, i.e.g/100 g), less than about 30 g/100 g, and less than about 15 g/100 g. Onthe other hand, typical specialty carbon black pigments have oilabsorptions ranging from about 150 g/100 g to more than 200 g/100 g.Thus, embodiments of the present black polysilocarb ceramic pigments canhave oil absorptions that are at least 13×, 5× or 3× lower than carbonblack pigments having the same or similar blackness.

Embodiments of the black polymer derived ceramic pigments can find usein many applications and industries. For example, the polysilocarbderived ceramic pigments provide high temperature resistancecapabilities, they are indoor/outdoor color fast, UV resistant, and areresistant to most chemicals, finding applications in harsh environments,such as marine and oil field environments. They are non-corrosive andnon-conductive, which enables uses beyond that which most black pigmentscould be utilized. These uses would include Industrial and residentialfurnace coatings; engine components as high heat resistant plastic partsor coatings on metal parts; pipe coatings; chemical plant equipmentcoatings; oil field coatings; residential barbeques; aftermarketcoatings; ceramic and glass inkjet inks; electronic coatings; batteryanodes; gun barrel coatings; PVC siding, metal roof coatings; colorationof ceramic parts for many end uses; space craft coatings; sand coatings;microwave curable elastomers, plastics, inks and coatings; cookware;hotplates; satellite components; high heat absorbing coatings;proprietary military coatings; high heat resistant potting compound;electrical insulation; Fluoropolymer elastomers for use as seals andgaskets in extremely harsh environments; high emissivity coatings,thermal protection systems, thermal barrier coatings, thermal imagingcoatings, injection-molded parts, thermoformed parts, transfer moldedparts, compression molded parts, rotational molded parts, blow-moldedparts, cast parts, vacuum formed parts, hot-isostatic pressed parts,sinterable parts, vacuum impregnated parts, impregnated fiber forms,woven fabrics, textiles, engineering textiles, woven fiber fabrics,fiber mats, wear resistant metal matrix composites, wear resistantceramic matrix composites, wear resistant polymer matrix composites,mixed oxide ceramics, refractory applications, and combinations andvariations of these and others.

Embodiments of the black polymer derived ceramic pigments are microwavesafe, e.g., they do not absorb and are not effect by microwaves. Typicalcarbon black pigments, are effected by microwaves, and cannot be used inmicrowave environments or applications.

In an embodiment of a process to make polymer derived ceramic pigment,and preferably to make a black polymer derived ceramic pigment, in themake-up segment a precursor formulation is metered into a one cubicmeter tank having an in-line mix at rate of about 0.22 cubic meters perhour along with a stream of the catalyst at a ratio of 1 part catalystto 100 parts precursor. The in-line mix tank is equipped with a highspeed mixer. Residence time in the mix tank is about twenty-fiveminutes. The polymerization reaction starts in the mix tank.

In this embodiment of the process, the forming and curing segments arecombined. Thus, the catalyzed precursor formulation, after mixing, iscontinuously feed to a drum, or a moving belt, e.g., a flaker belt, andpreferably a stainless steel flaker belt or other similar device.Nozzles, a drip trough, an elongated opening, or slice, or othermetering and distribution apparatus can be used to preferably obtain auniform distribution, including thickness, of the liquid precursor onthe moving belt. When the precursor is laid down onto the belt, theprecursor can be moving at the same speed as the belt, at a faster speedthan the belt (e.g., rushed), or at a slower speed than the belt (e.g.,dragged). As the liquid precursor is moved with the belt it is heated toa sufficient temperature to cure the precursor formulation to form acured material. For example, radiant heaters may be use above the belt,tunnel dryers may be used, the belt itself may be heated, e.g., withsteam or electric heaters, and combinations and variations of these andother apparatus and methods to heat and maintain the temperature of theprecursor material being carried on the belt. For example, in apreferred embodiment the belt is heated to about 100-200° C. by a steamcoil along the underside of the belt. The cross linking reaction, whichfirst began in the mixing tank, continues as the precursor travels alongthe belt to the point that it solidifies, preferably the precursor hasreached a predetermined and predicted cure amount, e.g., green cure,hard cure, final cure, by the time it reaches the end of the belt.Depending upon the precursor formulation, the amount of catalyst, thetemperature and other factors, the residence time on the belt can beabout 5 to about 60 minutes, more than about 10 minutes, more than about20 minutes, about 20 minutes, and more than about 40 minutes, andgreater and lesser durations.

In this embodiment, at the end of the belt, the cured precursor, e.g.,green material, falls from the belt and into a chopper, which reducesthe size of the green material to about ≦10 μm, about ≦100 μm, about≦200 μm, and about ≦500 μm, as well as other sizes. The chopped curedmaterial can be stored, in for example a storage hopper.

In this embodiment of the process, in the pyrolizing segment the polymerfrom the storage hopper is transferred to cars and fed to a furnace,e.g., a kiln, periodic (e.g., box) kiln, and preferably an oxygendeficient, natural gas fired tunnel kiln. The kiln is operated in anoxygen deficient regime to maintain a non-oxidizing atmosphere in thepolymer. The cars move through the kiln, preferably at a constant rate,which results in a three phase, 24-hour pyrolysis process, e.g., areforming process. In the first phase, the temperature of the polymer israised to 1000° C. over a period of 16 hours. At the end of the 16-hourramp period, it remains at this temperature, 1000° C., for two hours. Inthe final phase the material is air cooled to ambient temperature overthe next six hours. Through this pyrolizing segment of the process thecured material, e.g., green material, is converted to a ceramicmaterial. The ceramic material is removed, e.g., dumped from the kilncars into an intermediate storage hopper awaiting further processing.

In this embodiment of the processes, throughout the pyrolizing segment,the exhaust gases from the kiln are preferably ducted away to a cleaningor waste handling system, for example to a Vapor Destruction Unit (VDU)to destroy residual combustibles. The VDU can than be followed by othercleaning systems, such as for example, a wet scrubber to remove anyparticulates (predominately silica). The silica can then be removed fromthe water effluent and recovered for reuse, sale or proper disposal.After removal of the silica, the effluent from the scrubber can bereused for example in a grey water loop, further cleaned and reused, ortransferred to a waste water treatment facility for eventual discard.

In this embodiment of the process, in the post-processing segment threepost processing techniques are used—jet milling, bead milling and spraydrying. In many embodiments of applications for polymer derived ceramicpigments, and in particular for black polymer derived ceramic pigments,a particular particle size can be a factor, an application requirement,and in some instances a very important parameter for the pigment. Inthis embodiment, jet milling is the first stage of the size reductionprocess. Ceramic material having a particle size of about 300-500 μm, istaken from the intermediate storage; and is fed into the jet millingreceiver. At the jet milling receiver the ceramic material is directedto several, e.g., two, three, four or more, parallel mills. The jetmills reduce the particle size from 300-500 μm, to about 1-20 μm, about3 μm, and about 2 μm. The use of steam jet milling can reduce theparticle size to about 1 μm, less than about 1 μm and about 0.5 μm andpotentially smaller, these reductions in size can preferably be achievedun-surface treated, i.e., with out the need to provide a surfacetreatment to the larger particles prior to milling. The milled ceramiccan then be classified and those sizes not meeting the requirements forfurther processing can be removed and preferably repurposed. Forexample, about 10% of the product can be classified and sold at anintermediate size.

The remaining 90% of the jet mill product is transferred to the beadmill receiver for further size reduction. The 1-20 μm jet milled productis fed to a slurry tank where it is mixed with a liquid phase orsolvent, such as demineralized water, and a dispersant at a ratio ofapproximately 60 parts solids, 39 parts solvent and 1 part dispersant.The dispersant can be a soap, detergent, surfactant, fatty acid, naturaloil, synthetic oil, wetting agent, dispersing agent, natural andsynthetic oils, natural and synthetic glycols and polyglycols, modifiedwaxes and hydrocarbons. Dispersants function to stabilize the particlevia either steric, electrosteric, or electrostatic means and can benon-ionic, anionic, cationic, or zwitterionic. Structures can be linearpolymers and copolymers, head-tail type modified polymers andcopolymers, AB-block copolymers, ABA block copolymers, branched blockcopolymers, gradient copolymers, branched gradient copolymers,hyperbranched polymers and copolymers, star polymers and copolymers.BASF, Lubrizol, RT Vanderbilt, and BYK are all common manufacturers ofdispersants. Trade names include: Lubrizol Solsperse series, VanderbiltDarvan series, BASF Dispex series BYK DisperByk series, BYK LP-C 2XXXXseries. Grades can include BYK DisperByk 162, 181, 182, 190, 193, 2200,and 2152; LP-C 22091, 22092, 22116, 22118, 22120, 22121, 22124, 22125,22126, 22131, 22134, 22136, 22141, 22146, 22147, 22435; LP-N 22269;Solsperse 3000, Darvan C-N. A proper dispersant will provide goodreduction in viscosity from a high-solids content paste with <5%additive, causing it to become a flowable liquid instead of anon-flowable paste. The ratio of dispersant to ceramic solids can rangefrom about 0.01 wt % to 8 wt %, to 0.5 wt % to 4 wt %, 1 wt % to 3 wt %,and greater and lesser ratios. This slurry is fed, e.g., batch wise,semi-continuous or continuously, to single, to several parallel,two-stage bead milling systems, e.g., two, three, four, five or more.These mills may also have other mills serially connected to theiroutputs. Bead milling further reduces the particle size to less than 1μm, and preferably for submicron applications to a particle size ofabout ≦0.1 μm.

In this embodiment the wet product from the bead is fed to a spraydryer, which can be steam heated, gas heated, air, inert gas, orelectrically heated, where the water content is reduced to <1 percent.In the spray dryer, the 0.1 μm particles agglomerate to a 10-80 μmparticle size, e.g., agglomerate size, agglomerated particle size.Preferably, a batch, lot, or shipment of the agglomerate particles has amedian particle size distribution, e.g., D₅₀, of greater than about 10μm, greater than about 20 μm, and greater than about 50 μm. Preferablythese agglomerates are stable through the handling and shipping processand the unpacking and initial use for an application. In addition to thepreferred median particle size distribution of greater than 10 μm, themean agglomerate particle size may be from 10 μm or less, from about 10μm to about 80 μm, and may be larger than 80 μm.

In this embodiment the exhaust from the spray dryer goes through acyclone, followed by a bag filter to remove any particulates prior torelease to the atmosphere. The collected dust is recycled to the beadmill or spray dryer feed. The water or solvent evaporated from thepowder in the spray dryer is condensed, recovered and recycled to thebead mill feed slurry. The dry product from the spray dryer can bestored, packaged, shipped to users, or further processed or treated.

The product, e.g., the stored, packaged, shipped etc. pigment, can bein: a dry powered form; a dry agglomerate form; a sheet form, a block orother larger volumetric shape; a suspension having from about 20% solids(or less solids) to about 50% solids (or more), a paste, an aqueouspaste, an aqueous suspension, and combinations and variations of theseand other forms. For an embodiment of the product that is a dry powder,or dry agglomerate, the moisture content can be from about 0% to about10% moisture, about less than 5%, about less than 3%, and about lessthan 1%.

In the foregoing embodiment of a process to make polymer derived ceramicpigment, a preferable embodiment of the polymer derived ceramic pigmentis a black polysilocarb derived ceramic pigment. The black polysilocarbderived pigment can be used in many applications.

Polymer derived black ceramic pigments, and preferably blackpolysilocarb derived ceramic pigments have applications in, for example,coatings used on, or in, walls, appliances, automobiles, engines, pipes,grills, microwaves, cook wear, wires, printed circuit boards, human andanimal nails, cosmetics, pipes, interior of components such asautomobile components, food packaging and other devices, structurescomponents and articles. They have applications in coatings that provideend use features, such as for example, corrosion protection, abrasionprotection, skid resistance, decorative and astatic effects,photosensitive properties, UV protection, heat resistance andprotection, and combinations and variations of these and other features.They have applications in coating that are organic, inorganic andcombinations of these. They have applications in coatings that areporcelain, enamels, electroplated, to name a few others. They haveapplications in architectural coating, product coatings used by originalequipment manufacturers (“OEM coatings”), special purpose coatings andother types of coatings. Architectural coatings would include forexample paints and varnishes. Product coatings would include OEMcoatings, industrial coatings, industrial finishes, boats, water craft,ships, after market coatings, and repair/refurbishing coatings, theproducts to which product coatings are applied is essentially endless,and would include for example automobiles, aircraft, appliances, wire,pipes, furniture, metal cans, chewing gum wrappers, packaging,equipment, etc. Specialty coatings would include for example, specialtycoatings for cars, specialty marine coatings, stripping for highways,and others.

Polymer derived black ceramic pigments, and preferably blackpolysilocarb derived ceramic pigments have applications in coatingsembodiments that contain a binder, volatile components, a pigment (whichmay be solely one or more polymer derived black ceramic pigments orcombinations of the polymer derived black pigment and other pigments),and additives (noting that the polymer derived pigment, which may beother colors than black and preferably embodiments of polysilocarbpigments, which may be other colors than black, can function as, or are,additives). These pigments are used with all types of resin, includingacrylics, alkyds, amino, cellulosics, epoxies, polyesters, urethanes,poly(vinyl acetates), poly(vinyl chlorides), and others.

The polymer derived black ceramic pigments, and preferably blackpolysilocarb derived ceramic pigments can have surface properties andsizes such that they do not change the rheology of existing formulationsthat use other types of black pigments. In this manner they can bedirectly substituted for some, or all of the other type of pigment in aparticular formulation without changing the rheology of that formulationand providing for example improved blackness and opacity. The nature ofthese pigments also provides the ability to have an embodiment of thesepigments that provides functionality to control, modify, and regulatethe rheology of a formulation. In this manner these pigments would havea dual role in the formulation as a pigment and as a rheology controladditive.

Embodiments of coatings containing black polysilocarb derived ceramicpigments provided enhanced abrasion resistance, e.g., the wearing awayof a surface, and enhanced mar resistance, e.g., disturbances in thesurface that alters its appearance. Abrasion and mar resistance wouldinclude resistance to scratching, gouging, wearing, and generally theresistance to the detrimental effects that occur when two surfaces arein sliding contact. Coatings using the black polysilocarb derivedceramic pigments have abrasion resistance as measured by Taber AbrasionTester (reported as number of mg of coating worn off after 1,000 cycles)of at most 30 mg, at most 150 mg, from about 10 mg to about 200 mg, andgreater than 200 mg.

Embodiment of coatings containing black polysilocarb derived ceramicpigments provided enhanced hardness. Hardness for coatings typically ismeasured by way of indentations, scratch, and pendulum tests. Hardnesstests for coatings typically include an indentation test, the fallingball indentation Test (ASTM D-2394, which is well known to and availableto the art, and the entire disclosure of which is incorporated herein byreference), a scratch test, the pencil hardness test (ASTM-D-3363-00,which is well known to and available to the art, and the entiredisclosure of which is incorporated herein by reference), and a pendulumtest, the Sward rocker (ASTM-2134-93), which is well known to andavailable to the art, and the entire disclosure of which is incorporatedherein by reference).

Embodiment of Coatings using the black polysilocarb derived ceramicpigments have indentation test results of at least 100 inch pounds atleast 160 inch pounds, from about 50 to about 150 inch pounds, andgreater than 160 inch pounds. Coatings using the black polysilocarbderived ceramic pigments can have the same or better blackness, whilehaving increases in indentation test results of at least about 50 inchpounds, at least about 160 inch pounds, and greater, when compared to asimilar formulation using carbon black or metal oxides as the pigment.

Embodiments of coatings using the black polysilocarb derived ceramicpigments have scratch test results of at least 7B pencil, at least Fpencil, from about 8B pencil to about 6H pencil, and greater than 6Hpencil. Coatings using the black polysilocarb derived ceramic pigmentscan have the same or better blackness, while having increases in scratchtest results of at least about 7B pencil, at least about F pencil, andgreater, when compared to a similar formulation using carbon black ormetal oxides as the pigment.

Embodiments of coatings using the black polysilocarb derived ceramicpigments have pendulum test results of at least 20 oscillations at least25 oscillations, from about 15 to about 55 oscillations, and greaterthan 56 oscillations. Coatings using the black polysilocarb derivedceramic pigments can have the same or better blackness, while havingincreases in pendulum test results of at least about 20 oscillations, atleast about 50 oscillations, and greater, when compared to a similarformulation using carbon black or metal oxides as the pigment.

The polymer derived black ceramic pigments, and preferably blackpolysilocarb derived ceramic pigments can be used in formulations havingUV stabilizers. These pigments do not diminish or adversely affect theUV stabilizing ability performance of the UV stabilizers. It istheorized that the polysilocarb derived ceramic pigments may provideadded UV stabilization to these UV stabilized formulations. The UVstabilizers can be UV absorbers, UV quenchers, and combinations ofthese. Typical UV stabilizes include, for example,2-hydroxybenzophenones, 2-(2-hydroxyphenyl)-2H-benztriazoles,2-(2-hydroxyphenyl)-4,6-phenyl-1,3,5-triazines, benzylidenemalonates,oxalanilides and others.

Typically, embodiments of the polymer derived black ceramic pigments,and preferably black polysilocarb derived ceramic pigments can functionas a UV absorber, and can be added to coatings to provide thesefunction, thus function as both a additive and a pigment. Embodiments ofa 3.0 μm D₅₀ black polysilocarb derived ceramic pigment exhibit UVabsorption (e.g., absorption coefficient, e.g., absorptivity) based uponthe UV-vis data taken in diluted DI water solutions, set out in Table 1.The concentration of material is given in grams per 100 g of water(equivalently, g/100 mL). These concentrations gave a translucentsolution.

TABLE 1 absorption coefficient dB/cm/ dB/cm/ dB/cm/ concentrationconcentration concentration concentration (g/100 g) @ 300 nm @ 450 nm @800 nm 0.00952 3538.894732 3526.83657 3451.4463 0.02590 979.6193238961.519095 946.46022

Generally, embodiments of the polysilocarb derived ceramic pigment canhave absorption coefficients of greater than 500 dB/cm/(g/100 g),greater than 5,000 dB/cm/(g/100 g), greater than 10,000 dB/cm/(g/100 g),from about 500 dB/cm/(g/100 g) to about 1,000 dB/cm/(g/100 g), fromabout 1,000 to about 5,000 dB/cm/(g/100 g), and from about 500dB/cm/(g/100 g) to about 10,000 dB/cm/(g/100 g). In general, the smallerthe pigments size, for the same pigment the higher will be theabsorption coefficients.

The polymer derived black ceramic pigments, and preferably blackpolysilocarb derived ceramic pigments can be used in formulations havingantioxidants. These pigments do not diminish or adversely affect theanti-oxidizing performance of the antioxidants. It is theorized that thepolysilocarb derived ceramic pigments may provide added anti-oxidationprotection to these antioxidant containing formulations. Typicalantioxidants include for example preventive antioxidants, peroxidedecomposers, sulfides, phosphites, metal complex agents, and others.

The polymer derived black ceramic pigments, and preferably blackpolysilocarb derived ceramic pigments can be used in formulations havinghinder amine light stabilizers (“HALS”), which function to prevent thephoto oxidative degradation of coatings. These pigments do not diminishor adversely affect the photo-oxidizing performance of the HALS. It istheorized that the polysilocarb derived ceramic pigments may provideadded photo-oxidation protection to these HALS containing formulations.Further, the black polysilocarb derived ceramic pigments in someembodiments can be used to replace some, most, and all, of the HALS inthe coating.

The polymer derived black ceramic pigments, and preferably blackpolysilocarb derived ceramic pigments can be used in many types ofcoating or formulations, such as for example thermoplastic acrylicresins, thermosetting acrylic resins, hydroxy-functional acrylic resins,water reducible thermosetting acrylic resins, waterborne coatings (i.e.,any coating with an aqueous media, e.g., latex coatings), waterreducible coatings (i.e., a waterborne coating based on a resin havinghydrophilic groups in most or all of its molecules), water solublecoatings (i.e., are soluble in water), latexes, acrylic latexes, vinylester latexes, thermosetting latexes, polyester resins,hydroxy-terminated polyester resins, amino resins, aminoplast resins,baked thermosetting coatings, melamine-formaldehyde resins (e.g., classI and class II), urea-formaldehyde resins, benzoguanamine-formaldehyderesins, glycoluril-formaldehyde resins,poly(meth)acrylamide-formaldehyde resins, polyurethane resins, twopackage solvent borne urethane coatings, epoxy resins, waterborneepoxy-amine systems, drying oil based resins, varnishes, alkyd resins,silicones, silicone rubber resins, and tetraethylorthosilicate (TEOS)based resins, among others.

The polymer derived black ceramic pigments, and preferably blackpolysilocarb derived ceramic pigments can be used in many types ofcoating or formulations that utilize different types of solvents, suchas for example, weak hydrogen-bonding solvents (e.g., aliphatic andaromatic hydrocarbons), hydrogen-bond acceptor solvents (e.g., estersand ketones) and hydrogen-bond donor-acceptor solvents (e.g., alcoholsand propylene glycol).

In general, the smaller the particle size, the greater the fraction oflight that will be absorbed by the same quantity, i.e., weight ofparticles. For pigments, and generally for embodiments of the polymerderived black ceramic pigments, and preferably black polysilocarbderived ceramic pigments, the smaller the particle size of the pigmentthe greater the absorption of light.

The ability of a coating to hiding the substrate, i.e., hiding, is aproperty that can be affected by many factors. Generally, hidingincreases as film or coating thickness increases at the same pigmentloading. Lower hiding coatings require thicker films. Also, hidingincreases as pigment particle size decreases until a maximum hiding isreached and then hiding begins to decrease. Two coatings will hide thesubstrate the same, one with a lower pigment loading (of smallerparticle size) and one with a higher pigment loading of a largerparticle size. In general, embodiments of the polymer derived blackceramic pigments, and preferably black polysilocarb derived ceramicpigments, provide higher hiding coatings, or hiding ability, for thesame loading (e.g., weight of pigment to volume of coating) of blackmixed metal oxide pigments and more quickly approach the hiding power offurnace carbon black.

TABLE 2 Particle Pigment loading Pigment Type size (micron) to hidingPolySiloCarb 2.5 to 3.5 1 lb/gallon to 1.5 lbs/gallon PolySiloCarb 1.5to 2.5 0.8 lbs/gallon to 1 lb/gallon PolySiloCarb 1.0 to 1.5 0.7 to 0.8lbs/gallon PolySiloCarb 0.8 to 1.0 0.6 to 0.7 lbs/gallon PolySiloCarb0.6 to 0.8 0.55 to 0.60 lbs/gallon PolySiloCarb 0.4 to 0.6 0.45 to 0.55lbs/gallon PolySiloCarb 0.2 to 0.4 0.35 to 0.45 lbs/gallon PolySiloCarb0.1 to 0.2 0.25 to 0.35 lbs/gallon PolySiloCarb less than 0.1 less than0.25 lbs/gallon CI Black 28 about 0.5 about 0.5 lbs/gallon CI Black 26about 0.3 about 0.3 lbs/gallon Thermal 0.25 to 0.35 about 0.4 lbs/gallonCarbon Black FurnaceCarbon 0.03-0.05 0.1 to 0.2 lbs/gallon Black

Pigment loading to hiding is the required weight of pigment in a 50micron dry film coating to cover a black and white substrate such thatthe eye cannot differentiate a difference in color over either coloredbackground.

In general, in using the polymer derived black ceramic pigments, andpreferably the black polysilocarb derived ceramic pigments, they can beformulated, mixed or made into a concentrated composition that cantypically, although not necessarily, have other ingredients. Theseconcentrated compositions are typically liquids, although notnecessarily, they typically are call mill bases, dispersions, colorants,master-batches, and similar terms, which terms for the purposes of thisspecification, unless specifically stated otherwise, will be used tointerchangeably. The present black ceramic pigments have excellentwettability, separation properties, and stability properties in bothorganic and aqueous media.

Polymer derived ceramic mill bases can contain one embodiment of thepresent ceramic pigments, several different embodiments of the presentceramic pigments, other types of pigments, such as carbon black, andcombinations and variations of these. When more than one pigment ispresent the mill base can be referred to as a composite grind, orcomposite grind mill base. Thus, for example, an embodiment of a polymerderived ceramic a composite grind mill base has a black polysilocarbceramic pigment and one or more of the following pigments: organicpigments, such as arylamide yellow (PY 73), diarylide yellow, barium red2B toner (PR 48.1); polycyclic pigments, such as copper phthalocyanine,dioxanzine violet (PV 23), tetrachloro thiondigo (PR 88); inorganicpigments, such as carbon black, titanium dioxide, iron oxides, azurite,cadmium sulphides.

Although in embodiments of the present black ceramic pigments,dispersants are not needed or required, they may be added to either themill base, or with the mill base at the time it is added to the coatingformulation. Dispersants such as polymeric dispersants, A-B copolymerdispersants, hyperdispersants, superdispersants, and others may be used.In general dispersants function to stabilize the particle via eithersteric, electrosteric, or electrostatic means and can be non-ionic,anionic, cationic, or zwitterionic. Embodiments of dispersant structurescan be linear polymers and copolymers, head-tail type modified polymersand copolymers, AB-block copolymers, ABA block copolymers, branchedblock copolymers, gradient copolymers, branched gradient copolymers,hyperbranched polymers and copolymers, star polymers and copolymers, andcombinations and various of these and others.

It being understood that the mill base can be prepared and stored forlater use, shipped, or used immediately. Further the step of making amill base may be combined with, a part of, or otherwise incorporatedinto the process of formulation and making the coating. Generally inmaking a polymer derived ceramic pigmented coating three steps typicallymay be used—premixing, e.g., stirring the dry pigment into a liquidvehicle and eliminating any lumps; imparting shear stress to separatethe pigment aggregates, which may be done in the presence of adispersion stabilizer; and, letting down, which entails combining thepigment dispersion, e.g., mill base, with the remainder of theingredients for the coating formulation. It being understood that someequipment is capable of performing only one or two of the steps, whileother are capable of performing all three steps.

Equipment that may be used for forming the mill base can include, forexample, high-speed disk dispersers, rotor-stator mixers, ball mills,basket mills, shot mills, hammer mills, media mills (e.g., sand mills,shot mills, bead mills), three roll mills, two roll mills, extruders,kneaders, internal batch mixers, such as banbury machines, extruders,ultrasound dispersers, and others.

The polymer derived black ceramic pigments, and preferably the blackpolysilocarb derived ceramic pigments can be used to make tinting pastesin this manner providing an embodiment of a polymer derived tintingpaste. In general tinting paste will have a high loading of pigment to asmall amount of resin so that a small amount of paste will give themaximum color. The polymer derived black ceramic pigments, andpreferably the black polysilocarb derived ceramic pigments improve thetint strength as the particle size decreases. In general, tintingembodiments of the polymer derived black ceramic pigments, andpreferably black polysilocarb derived ceramic pigments, provide highertinting strength in coatings, (less black pigment required to reach thesame grey color with a lightness value between 72 and 75 on the CIELABLab scale, the lightness coming from a larger amount of TiO₂ whitepigment which is tinted to a grey color by small additions of the blackpigment). The smaller particle size polymer derived black ceramicpigment has higher tinting strength than black mixed metal oxidepigments and more quickly approaches the tinting strength of furnacecarbon black. Tinting pastes can use multiple black additives, includingpolysilocarb materials.

TABLE 3 Particle Pigment loading Pigment Type size (micron) to lightgrey PolySiloCarb 2.5 to 3.5 12 to 15 parts PolySiloCarb 1.5 to 2.5 11to 12 parts PolySiloCarb 1.0 to 1.5 10 to 11 parts PolySiloCarb 0.8 to1.0 9 to 10 parts PolySiloCarb 0.6 to 0.8 7.5 to 9 parts PolySiloCarb0.4 to 0.6 6.5 to 7.5 parts PolySiloCarb 0.2 to 0.4 4.5 to 6.5 partsPolySiloCarb 0.1 to 0.2 2.5 to 4.5 parts PolySiloCarb less than 0.1 lessthan 2.5 parts CI Black 28 about 0.5 7 to 8 parts CI Black 26 about 0.33.5 to 4.5 parts FurnaceCarbon 0.03-0.05 1 part Black

It should be understood that the use of headings in this specificationis for the purpose of clarity, reference, and is not limiting in anyway. Thus, the processes compositions, and disclosures described under aheading should be read in context with the entirely of thisspecification, including the various examples. The use of headings inthis specification should not limit the scope of protection afford thepresent inventions.

General Processes for Obtaining a Polysilocarb Precursor

Typically polymer derived ceramic precursor formulations, and inparticular polysilocarb precursor formulations can generally be made bythree types of processes, although other processes, and variations andcombinations of these processes may be utilized. These processesgenerally involve combining precursors to form a precursor formulation.One type of process generally involves the mixing together of precursormaterials in preferably a solvent free process with essentially nochemical reactions taking place, e.g., “the mixing process.” The othertype of process generally involves chemical reactions, e.g., “thereaction type process,” to form specific, e.g., custom, precursorformulations, which could be monomers, dimers, trimers and polymers. Athird type of process has a chemical reaction of two or more componentsin a solvent free environment, e.g., “the reaction blending typeprocess.” Generally, in the mixing process essentially all, andpreferably all, of the chemical reactions take place during subsequentprocessing, such as during curing, pyrolysis and both.

It should be understood that these terms—reaction type process, reactionblending type process, and the mixing type process—are used forconvenience and as a short hand reference. These terms are not, andshould not be viewed as, limiting. For example, the reaction process canbe used to create a precursor material that is then used in the mixingprocess with another precursor material.

These process types are described in this specification, among otherplaces, under their respective headings. It should be understood thatthe teachings for one process, under one heading, and the teachings forthe other processes, under the other headings, can be applicable to eachother, as well as, being applicable to other sections, embodiments andteachings in this specification, and vice versa. The starting orprecursor materials for one type of process may be used in the othertype of processes. Further, it should be understood that the processesdescribed under these headings should be read in context with theentirely of this specification, including the various examples andembodiments.

It should be understood that combinations and variations of theseprocesses may be used in reaching a precursor formulation, and inreaching intermediate, end and final products. Depending upon thespecific process and desired features of the product the precursors andstarting materials for one process type can be used in the other. Aformulation from the mixing type process may be used as a precursor, orcomponent in the reaction type process, or the reaction blending typeprocess. Similarly, a formulation from the reaction type process may beused in the mixing type process and the reaction blending process.Similarly, a formulation from the reaction blending type process may beused in the mixing type process and the reaction type process. Thus, andpreferably, the optimum performance and features from the otherprocesses can be combined and utilized to provide a cost effective andefficient process and end product. These processes provide greatflexibility to create custom features for intermediate, end, and finalproducts, and thus, any of these processes, and combinations of them,can provide a specific predetermined product. In selecting which type ofprocess is preferable, factors such as cost, controllability, shelflife, scale up, manufacturing ease, etc., can be considered.

In addition to being commercially available the precursors may be madeby way of an alkoxylation type process, e.g., an ethoxylation process.In this process chlorosilanes are reacted with ethanol in the presencesof a catalysis, e.g., HCl, to provide the precursor materials, whichmaterials may further be reacted to provide longer chain precursors.Other alcohols, e.g., methanol may also be used. Thus, for exampleSiCl₄, SiCl₃H, SiCl₂(CH₃)₂, SiCl₂(CH₃)H, Si(CH₃)3Cl, Si(CH₃)ClH, arereacted with ethanol CH₃CH₂OH to form precursors. In some of thesereactions phenols may be the source of the phenoxy group, which issubstituted for a hydride group that has been placed on the silicon.One, two or more step reactions may need to take place.

Precursor materials may also be obtained by way of an acetylene reactionroute. In general there are several known paths for adding acetylene toSi—H. Thus, for example, tetramethylcyclotetrasiloxane can be reactedwith acetylene in the presence of a catalyst to producetetramethyltetravinylcyclotetrasiloxane. This product can then be ringopened and polymerized in order to form linear vinyl, methylsiloxanes.Alternatively, typical vinyl silanes can be produced by reacting methyl,dichlorosilane (obtained from the direct process or Rochow process) withacetylene. These monomers can then be purified (because there may besome scrambling) to form vinyl, methyl, dichlorosilane. Then the vinylmonomer can be polymerized via hydrolysis to form many cyclic, andlinear siloxanes, having various chain lengths, including for examplevarious cyclotetrasiloxanes (e.g., D₄′) and various cyclopentasiloxanes(e.g., D₅′). These paths, however, are costly, and there has been a longstanding and increasing need for a lower cost raw material source toproduce vinyl silanes. Prior to the present inventions, it was notbelieved that MHF could be used in an acetylene addition process toobtain vinyl silanes. MHF is less expensive than vinyl, methyl (eitherlinear or cyclic), and adding acetylene to MHF to make vinyl meets,among other things, the long standing need to provide a more costeffective material and at relatively inexpensive costs. In making thisaddition the following variables, among others, should be considered andcontrolled: feed (D₄′, linear methyl, hydrogen siloxane fluids);temperature; ratio of acetylene to Si—H; homogeneous catalysts(Karstedt's, DBT Laureate, no catalyst, Karstedt's with inhibitor);supported catalysts (Pt on carbon, Pt on alumina, Pd on alumina); flowrates (liquid feed, acetylene feed); pressure; and, catalystconcentration. Examples of embodiments of reactions providing for theaddition of acetylene to MHF (cyclic and linear) are provided in TablesA and B. Table A are batch acetylene reactions. Table B are continuousacetylene reactions. It should be understood that batch, continuous,counter current flow of MHF and acetylene feeds, continuous recycle ofsingle pass material to achieve higher conversions, and combinations andvariations of these and other processes can be utilized.

TABLE A Batch Acetylene Reactions Methyl Amount of Acetylene ReactionAcetyl Mol % Hydride Catalyst % Solvent Temp Flow Time (rel to Total RunSi—H (grams) (rel to MeH) Inhibitor Solvent (grams) (° C.) (ccm) (hrs)Hydride) 1 MHF 400 0.48% 0.00% — —  80-100 — 0.20 — 2 MHF 1000 0.27%0.00% — — 65-75 276-328 0.75 3.4% 3 MHF 1000 0.00% 0.00% — — 80 378-7296.33 49.4% 100  120  4 MHF 117 0.20% 0.00% Hexane 1000  60-66 155-2424.50 188.0% 5 MHF 1000 0.40% 0.40% — — 55-90 102 7.5 15.7% 6 MHF 3601.00% 0.00% Hexane 392 65 102 6.4 40.3%  7a MHF 360 0.40% 0.00% Hexane400 65 — 2.0 23.4%  7b MHF 280 0.40% 0.00% Hexane 454 68 — 137.0 23.4% 8D4′ 1000 0.27% 0.00% — — 79 327-745 6.5 61.3% 9 MHF 370 0.40% 0.00%Hexane 402 65 155-412 8.0 140.3%

TABLE B Continuous Acetylene Reactions Reactor Reactor Acetyl Mol %Catalyst % Silane Conc Temp Pressure (rel to Total Run Si—H (rel to MeH)Inhibitor (wt %) Solvent (° C.) (psig) Hydride) 10 D4′ 5% Pt on 0.00%100.0% —  60-100 50 40.0% Carbon 11 D4′ 5% Pt on 0.00% 100.0% — 50-90100  20.0% Carbon 12 D4′ 1% Pt on 0.00% 100.0% — 40-50 50 23.8% Alumina13 MHF 5% Pt on 0.00% 100.0% — 55-60 55-60 13.6% Carbon 14 MHF 0.01% Pton 0.00% 20.0% Hexane 20-25 50 108.5% Alumina 15 MHF 0.01% Pt on 0.00%20.0% Hexane 60 50-55 117.1% Alumina 16 MHF 0.01% Pt on 0.00% 20.0%Hexane 70 50 125.1% Alumina 17 MHF 0.12% Pt on 0.00% 20.0% Hexane 60 50133.8% Alumina 18 MHF 0.12% Pt on 0.00% 4.0% Hexane 60 50 456.0% Alumina(D4′ is tetramethyl tetrahydride cyclotetrasiloxane)

Continuous High Pressure Reactor (“CHPR”) embodiments may beadvantageous for, among other reasons: reaction conversion saving moreacetylene needed in liquid phase; tube reactors providing pressureswhich in turn increases solubility of acetylene; reaction with hexynesaving concentration and time (e.g., 100 hours,); can eliminatehomogeneous catalyst and thus eliminate hydrosilylation reaction withresultant vinyls once complete; and, using a heterogeneous (Solid)catalyst to maintain product integrity, increased shelf-life, increasepot-life and combinations and variations of these.

In addressing the various conditions in the acetylene additionreactions, some factors may be: crosslinking retardation by dilution,acetylene and lower catalyst concentration; and conversion (usingheterogeneous catalyst) may be lower for larger linear moleculescompared to smaller molecules.

The presence and quality of vinyl and vinyl conversions can bedetermined by, among other things: FT-IR for presence of vinylabsorptions, decrease in SiH absorption; ¹H NMR for presence of vinylsand decrease in SiH; ¹³C NMR for presence of vinyls.

As used herein, unless specified otherwise the terms %, weight % andmass % are used interchangeably and refer to the weight of a firstcomponent as a percentage of the weight of the total, e.g., formulation,mixture, material or product. As used herein, unless specified otherwise“volume %” and “% volume” and similar such terms refer to the volume ofa first component as a percentage of the volume of the total, e.g.,formulation, material or product.

The Mixing Type Process

Precursor materials may be methyl hydrogen, and substituted and modifiedmethyl hydrogens, siloxane backbone additives, reactive monomers,reaction products of a siloxane backbone additive with a silane modifieror an organic modifier, and other similar types of materials, such assilane based materials, silazane based materials, carbosilane basedmaterials, phenol/formaldehyde based materials, and combinations andvariations of these. The precursors are preferably liquids at roomtemperature, although they may be solids that are melted, or that aresoluble in one of the other precursors. (In this situation, however, itshould be understood that when one precursor dissolves another, it isnevertheless not considered to be a “solvent” as that term is used withrespect to the prior art processes that employ non-constituent solvents,e.g., solvents that do not form a part or component of the end product,are treated as waste products, and both.)

The precursors are mixed together in a vessel, preferably at roomtemperature. Preferably, little, and more preferably no solvents, e.g.,water, organic solvents, polar solvents, non-polar solvents, hexane,THF, toluene, are added to this mixture of precursor materials.Preferably, each precursor material is miscible with the others, e.g.,they can be mixed at any relative amounts, or in any proportions, andwill not separate or precipitate. At this point the “precursor mixture”or “polysilocarb precursor formulation” is compete (noting that if onlya single precursor is used the material would simply be a “polysilocarbprecursor” or a “polysilocarb precursor formulation” or a“formulation”). Although complete, fillers and reinforcers may be addedto the formulation. In preferred embodiments of the formulation,essentially no, and more preferably no chemical reactions, e.g.,crosslinking or polymerization, takes place within the formulation, whenthe formulation is mixed, or when the formulation is being held in avessel, on a prepreg, or over a time period, prior to being cured.

The precursors can be mixed under numerous types of atmospheres andconditions, e.g., air, inert, N₂, Argon, flowing gas, static gas,reduced pressure, elevated pressure, ambient pressure, and combinationsand variations of these.

Additionally, inhibitors such as cyclohexane, 1-Ethynyl-1-cyclohexanol(which may be obtained from ALDRICH), Octamethylcyclotetrasiloxane, andtetramethyltetravinylcyclotetrasiloxane, may be added to thepolysilocarb precursor formulation, e.g., an inhibited polysilocarbprecursor formulation. It should be noted thattetramethyltetravinylcyclotetrasiloxane may act as both a reactant and areaction retardant (e.g., an inhibitor), depending upon the amountpresent and temperature, e.g., at room temperature it is a retardant andat elevated temperatures it is a reactant. Other materials, as well, maybe added to the polysilocarb precursor formulation, e.g., a filledpolysilocarb precursor formulation, at this point in processing,including fillers such as SiC powder, carbon black, sand, polymerderived ceramic particles, pigments, particles, nano-tubes, whiskers, orother materials, discussed in this specification or otherwise known tothe arts. Further, a formulation with both inhibitors and fillers wouldbe considered an inhibited, filled polysilocarb precursor formulation.

Depending upon the particular precursors and their relative amounts inthe polysilocarb precursor formulation, polysilocarb precursorformulations may have shelf lives at room temperature of greater than 12hours, greater than 1 day, greater than 1 week, greater than 1 month,and for years or more. These precursor formulations may have shelf livesat high temperatures, for example, at about 90° F., of greater than 12hours, greater than 1 day, greater than 1 week, greater than 1 month,and for years or more. The use of inhibitors may further extend theshelf life in time, for higher temperatures, and combinations andvariations of these. The use of inhibitors, may also have benefits inthe development of manufacturing and commercial processes, bycontrolling the rate of reaction, so that it takes place in the desiredand intended parts of the process or manufacturing system.

As used herein the term “shelf life” should be given its broadestpossible meaning, unless specified otherwise, and would include, forexample, the formulation being capable of being used for its intendedpurpose, or performing, e.g., functioning, for its intended use, at 100%percent as well as a freshly made formulation, at least about 90% aswell as a freshly made formulation, at least about 80% as well as afreshly made formulation, and at at least about 70% as well as a freshlymade formulation.

Precursors and precursor formulations are preferably non-hazardousmaterials. They have flash points that are preferably above about 70°C., above about 80° C., above about 100° C. and above about 300° C., andabove. Preferably, they may be noncorrosive. Preferably, they may have alow vapor pressure, may have low or no odor, and may be non- or mildlyirritating to the skin.

A catalyst or initiator may be used, and can be added at the time of,prior to, shortly before, or at an earlier time before the precursorformulation is formed or made into a structure, prior to curing. Thecatalysis assists in, advances, and promotes the curing of the precursorformulation to form a preform.

The time period where the precursor formulation remains useful forcuring after the catalysis is added is referred to as “pot life”, e.g.,how long can the catalyzed formulation remain in its holding vesselbefore it should be used. Depending upon the particular formulation,whether an inhibitor is being used, and if so the amount being used,storage conditions, e.g., temperature, low O₂ atmosphere, andpotentially other factors, precursor formulations can have pot lives,for example, of from about 5 minutes to about 10 days, about 1 day toabout 6 days, about 4 to 5 days, about 30 minutes, about 15 minutes,about 1 hour to about 24 hours, and about 12 hours to about 24 hours.

The catalyst can be any platinum (Pt) based catalyst, which can, forexample, be diluted to a ranges of: about 0.01 parts per million (ppm)Pt to about 250 ppm Pt, about 0.03 ppm Pt, about 0.1 ppm Pt, about 0.2ppm Pt, about 0.5 ppm Pt, about 0.02 to 0.5 ppm Pt, about 1 ppm to 200ppm Pt and preferably, for some applications and embodiments, about 5ppm to 50 ppm Pt. The catalyst can be a peroxide based catalyst with,for example, a 10 hour half life above 90 C at a concentration ofbetween 0.1% to 3% peroxide, and about 0.5% and 2% peroxide. It can bean organic based peroxide. It can be any organometallic catalyst capableof reacting with Si—H bonds, Si—OH bonds, or unsaturated carbon bonds,these catalysts may include: dibutyltin dilaurate, zinc octoate,peroxides, organometallic compounds of for example titanium, zirconium,rhodium, iridium, palladium, cobalt or nickel. Catalysts may also be anyother rhodium, rhenium, iridium, palladium, nickel, and ruthenium typeor based catalysts. Combinations and variations of these and othercatalysts may be used. Catalysts may be obtained from ARKEMA under thetrade name LUPEROX, e.g., LUPEROX 231; and from Johnson Matthey underthe trade names: Karstedt's catalyst, Ashby's catalyst, Speier'scatalyst.

Further, custom and specific combinations of these and other catalystsmay be used, such that they are matched to specific formulations, and inthis way selectively and specifically catalyze the reaction of specificconstituents. Moreover, the use of these types of matchedcatalyst-formulations systems may be used to provide predeterminedproduct features, such as for example, pore structures, porosity,densities, density profiles, high purity, ultra high purity, and othermorphologies or features of cured structures and ceramics.

In this mixing type process for making a precursor formulation,preferably chemical reactions or molecular rearrangements only takeplace during the making of the starting materials, the curing process,and in the pyrolizing process. Chemical reactions, e.g.,polymerizations, reductions, condensations, substitutions, take place orare utilized in the making of a starting material or precursor. Inmaking a polysilocarb precursor formulation by the mixing type process,preferably no and essentially no, chemical reactions and molecularrearrangements take place. These embodiments of the present mixing typeprocess, which avoid the need to, and do not, utilize a polymerizationor other reaction during the making of a precursor formulation, providessignificant advantages over prior methods of making polymer derivedceramics. Preferably, in the embodiments of these mixing type offormulations and processes, polymerization, crosslinking or otherchemical reactions take place primarily, preferably essentially, andmore preferably solely during the curing process.

The precursor may be a siloxane backbone additive, such as, methylhydrogen (MH), which formula is shown below.

The MH may have a molecular weight (“mw” which can be measured as weightaveraged molecular weight in amu or as g/mol) from about 400 mw to about10,000 mw, from about 600 mw to about 3,000 mw, and may have a viscositypreferably from about 20 cps to about 60 cps. The percentage ofmethylsiloxane units “X” may be from 1% to 100%. The percentage of thedimethylsiloxane units “Y” may be from 0% to 99%. This precursor may beused to provide the backbone of the cross-linked structures, as well as,other features and characteristics to the cured preform and ceramicmaterial. This precursor may also, among other things, be modified byreacting with unsaturated carbon compounds to produce new, oradditional, precursors. Typically, methyl hydrogen fluid (MHF) hasminimal amounts of “Y”, and more preferably “Y” is for all practicalpurposes zero.

The precursor may be a siloxane backbone additive, such as vinylsubstituted polydimethyl siloxane, which formula is shown below.

This precursor may have a molecular weight (mw) from about 400 mw toabout 10,000 mw, and may have a viscosity preferably from about 50 cpsto about 2,000 cps. The percentage of methylvinylsiloxane units “X” maybe from 1% to 100%. The percentage of the dimethylsiloxane units “Y” maybe from 0% to 99%. Preferably, X is about 100%. This precursor may beused to decrease cross-link density and improve toughness, as well as,other features and characteristics to the cured preform and ceramicmaterial.

The precursor may be a siloxane backbone additive, such as vinylsubstituted and vinyl terminated polydimethyl siloxane, which formula isshown below.

This precursor may have a molecular weight (mw) from about 500 mw toabout 15,000 mw, and may preferably have a molecular weight from about500 mw to 1,000 mw, and may have a viscosity preferably from about 10cps to about 200 cps. The percentage of methylvinylsiloxane units “X”may be from 1% to 100%. The percentage of the dimethylsiloxane units “Y”may be from 0% to 99%. This precursor may be used to provide branchingand decrease the cure temperature, as well as, other features andcharacteristics to the cured preform and ceramic material.

The precursor may be a siloxane backbone additive, such as vinylsubstituted and hydrogen terminated polydimethyl siloxane, which formulais shown below.

This precursor may have a molecular weight (mw) from about 300 mw toabout 10,000 mw, and may preferably have a molecular weight from about400 mw to 800 mw, and may have a viscosity preferably from about 20 cpsto about 300 cps. The percentage of methylvinylsiloxane units “X” may befrom 1% to 100%. The percentage of the dimethylsiloxane units “Y” may befrom 0% to 99%. This precursor may be used to provide branching anddecrease the cure temperature, as well as, other features andcharacteristics to the cured preform and ceramic material.

The precursor may be a siloxane backbone additive, such as allylterminated polydimethyl siloxane, which formula is shown below.

This precursor may have a molecular weight (mw) from about 400 mw toabout 10,000 mw, and may have a viscosity preferably from about 40 cpsto about 400 cps. The repeating units are the same. This precursor maybe used to provide UV curability and to extend the polymeric chain, aswell as, other features and characteristics to the cured preform andceramic material.

The precursor may be a siloxane backbone additive, such as vinylterminated polydimethyl siloxane, which formula is shown below.

This precursor may have a molecular weight (mw) from about 200 mw toabout 5,000 mw, and may preferably have a molecular weight from about400 mw to 1,500 mw, and may have a viscosity preferably from about 10cps to about 400 cps. The repeating units are the same. This precursormay be used to provide a polymeric chain extender, improve toughness andto lower cure temperature down to for example room temperature curing,as well as, other features and characteristics to the cured preform andceramic material.

The precursor may be a siloxane backbone additive, such as silanol(hydroxy) terminated polydimethyl siloxane, which formula is shownbelow.

This precursor may have a molecular weight (mw) from about 400 mw toabout 10,000 mw, and may preferably have a molecular weight from about600 mw to 1,000 mw, and may have a viscosity preferably from about 30cps to about 400 cps. The repeating units are the same. This precursormay be used to provide a polymeric chain extender, a tougheningmechanism, can generate nano- and micro-scale porosity, and allowscuring at room temperature, as well as other features andcharacteristics to the cured preform and ceramic material.

The precursor may be a siloxane backbone additive, such as silanol(hydroxy) terminated vinyl substituted dimethyl siloxane, which formulais shown below.

This precursor may have a molecular weight (mw) from about 400 mw toabout 10,000 mw, and may preferably have a molecular weight from about600 mw to 1,000 mw, and may have a viscosity preferably from about 30cps to about 400 cps. The percentage of methylvinylsiloxane units “X”may be from 1% to 100%. The percentage of the dimethylsiloxane units “Y”may be from 0% to 99%. This precursor may be used, among other things,in a dual-cure system; in this manner the dual-cure can allow the use ofmultiple cure mechanisms in a single formulation. For example, bothcondensation type cure and addition type cure can be utilized. This, inturn, provides the ability to have complex cure profiles, which forexample may provide for an initial cure via one type of curing and afinal cure via a separate type of curing.

The precursor may be a siloxane backbone additive, such as hydrogen(hydride) terminated polydimethyl siloxane, which formula is shownbelow.

This precursor may have a molecular weight (mw) from about 200 mw toabout 10,000 mw, and may preferably have a molecular weight from about500 mw to 1,500 mw, and may have a viscosity preferably from about 20cps to about 400 cps. The repeating units are the same. This precursormay be used to provide a polymeric chain extender, as a tougheningagent, and it allows lower temperature curing, e.g., room temperature,as well as, other features and characteristics to the cured preform andceramic material.

The precursor may be a siloxane backbone additive, such as di-phenylterminated siloxane, which formula is shown below.

Where here R is a reactive group, such as vinyl, hydroxy, or hydride.This precursor may have a molecular weight (mw) from about 500 mw toabout 2,000 mw, and may have a viscosity preferably from about 80 cps toabout 300 cps. The percentage of methyl-R-siloxane units “X” may be from1% to 100%. The percentage of the dimethylsiloxane units “Y” may be from0% to 99%. This precursor may be used to provide a toughening agent, andto adjust the refractive index of the polymer to match the refractiveindex of various types of glass, to provide for example transparentfiberglass, as well as, other features and characteristics to the curedpreform and ceramic material.

The precursor may be a siloxane backbone additive, such as a mono-phenylterminated siloxane, which formulas are shown below.

Where R is a reactive group, such as vinyl, hydroxy, or hydride. Thisprecursor may have a molecular weight (mw) from about 500 mw to about2,000 mw, and may have a viscosity preferably from about 80 cps to about300 cps. The percentage of methyl-R-siloxane units “X” may be from 1% to100%. The percentage of the dimethylsiloxane units “Y” may be from 0% to99%. This precursor may be used to provide a toughening agent and toadjust the refractive index of the polymer to match the refractive indexof various types of glass, to provide for example transparentfiberglass, as well as, other features and characteristics to the curedpreform and ceramic material.

The precursor may be a siloxane backbone additive, such as diphenyldimethyl polysiloxane, which formula is shown below.

This precursor may have a molecular weight (mw) from about 500 mw toabout 20,000 mw, and may have a molecular weight from about 800 to about4,000, and may have a viscosity preferably from about 100 cps to about800 cps. The percentage of dimethylsiloxane units “X” may be from 25% to95%. The percentage of the diphenyl siloxane units “Y” may be from 5% to75%. This precursor may be used to provide similar characteristics tothe mono-phenyl terminated siloxane, as well as, other features andcharacteristics to the cured preform and ceramic material.

The precursor may be a siloxane backbone additive, such as vinylterminated diphenyl dimethyl polysiloxane, which formula is shown below.

This precursor may have a molecular weight (mw) from about 400 mw toabout 20,000 mw, and may have a molecular weight from about 800 to about2,000, and may have a viscosity preferably from about 80 cps to about600 cps. The percentage of dimethylsiloxane units “X” may be from 25% to95%. The percentage of the diphenyl siloxane units “Y” may be from 5% to75%. This precursor may be used to provide chain extension, tougheningagent, changed or altered refractive index, and improvements to hightemperature thermal stability of the cured material, as well as, otherfeatures and characteristics to the cured preform and ceramic material.

The precursor may be a siloxane backbone additive, such as hydroxyterminated diphenyl dimethyl polysiloxane, which formula is shown below.

This precursor may have a molecular weight (mw) from about 400 mw toabout 20,000 mw, and may have a molecular weight from about 800 to about2,000, and may have a viscosity preferably from about 80 cps to about400 cps. The percentage of dimethylsiloxane units “X” may be from 25% to95%. The percentage of the diphenyl siloxane units “Y” may be from 5% to75%. This precursor may be used to provide chain extension, tougheningagent, changed or altered refractive index, and improvements to hightemperature thermal stability of the cured material, can generate nano-and micro-scale porosity, as well as other features and characteristicsto the cured preform and ceramic material.

A variety of cyclosiloxanes can be used as reactive molecules in theformulation. They can be described by the following nomenclature systemor formula: D_(x)D*_(y), where “D” represents a dimethyl siloxy unit and“D*” represents a substituted methyl siloxy unit, where the “*” groupcould be vinyl, allyl, hydride, hydroxy, phenyl, styryl, alkyl,cyclopentadienyl, or other organic group, x is from 0-8, y is >=1, andx+y is from 3-8.

The precursor batch may also contain non-silicon based cross-linkingagents, be the reaction product of a non-silicon based cross linkingagent and a siloxane backbone additive, and combinations and variationof these. The non-silicon based cross-linking agents are intended to,and provide, the capability to cross-link during curing. For example,non-silicon based cross-linking agents that can be used include:cyclopentadiene (CP), methylcyclopentadiene (MeCP), dicyclopentadiene(“DCPD”), methyldicyclopentadiene (MeDCPD), tricyclopentadiene (TCPD),piperylene, divnylbenzene, isoprene, norbornadiene, vinylnorbornene,propenylnorbornene, isopropenylnorbornene, methylvinylnorbornene,bicyclononadiene, methylbicyclononadiene, propadiene,4-vinylcyclohexene, 1,3-heptadiene, cycloheptadiene, 1,3-butadiene,cyclooctadiene and isomers thereof. Generally, any hydrocarbon thatcontains two (or more) unsaturated, C═C, bonds that can react with aSi—H, Si—OH, or other Si bond in a precursor, can be used as across-linking agent. Some organic materials containing oxygen, nitrogen,and sulphur may also function as cross-linking moieties.

The precursor may be a reactive monomer. These would include molecules,such as tetramethyltetravinylcyclotetrasiloxane (“TV”), which formula isshown below.

This precursor may be used to provide a branching agent, athree-dimensional cross-linking agent, as well as, other features andcharacteristics to the cured preform and ceramic material. (It is alsonoted that in certain formulations, e.g., above 2%, and certaintemperatures, e.g., about from about room temperature to about 60° C.,this precursor may act as an inhibitor to cross-linking, e.g., in mayinhibit the cross-linking of hydride and vinyl groups.)

The precursor may be a reactive monomer, for example, such as trivinylcyclotetrasiloxane,

divinyl cyclotetrasiloxane,

trivinyl monohydride cyclotetrasiloxane,

divinyl dihydride cyclotetrasiloxane,

and a hexamethyl cyclotetrasiloxane, such as,

The precursor may be a silane modifier, such as vinyl phenyl methylsilane, diphenyl silane, diphenyl methyl silane, and phenyl methylsilane (some of which may be used as an end capper or end terminationgroup). These silane modifiers can provide chain extenders and branchingagents. They also improve toughness, alter refractive index, and improvehigh temperature cure stability of the cured material, as well asimproving the strength of the cured material, among other things. Aprecursor, such as diphenyl methyl silane, may function as an endcapping agent, that may also improve toughness, alter refractive index,and improve high temperature cure stability of the cured material, aswell as, improving the strength of the cured material, among otherthings.

The precursor may be a reaction product of a silane modifier with avinyl terminated siloxane backbone additive. The precursor may be areaction product of a silane modifier with a hydroxy terminated siloxanebackbone additive. The precursor may be a reaction product of a silanemodifier with a hydride terminated siloxane backbone additive. Theprecursor may be a reaction product of a silane modifier with TV. Theprecursor may be a reaction product of a silane. The precursor may be areaction product of a silane modifier with a cyclosiloxane, taking intoconsideration steric hindrances. The precursor may be a partiallyhydrolyzed tetraethyl orthosilicate, such as TES 40 or Silbond 40. Theprecursor may also be a methylsesquisiloxane such as SR-350 availablefrom General Electric Company, Wilton, Conn. The precursor may also be aphenyl methyl siloxane such as 604 from Wacker Chemie AG. The precursormay also be a methylphenylvinylsiloxane, such as H62 C from WackerChemie AG.

The precursors may also be selected from the following: SiSiB® HF2020,TRIMETHYLSILYL TERMINATED METHYL HYDROGEN SILICONE FLUID 63148-57-2;SiSiB® HF2050 TRIMETHYLSILYL TERMINATED METHYLHYDROSILOXANEDIMETHYLSILOXANE COPOLYMER 68037-59-2; SiSiB® HF2060 HYDRIDE TERMINATEDMETHYLHYDROSILOXANE DIMETHYLSILOXANE COPOLYMER 69013-23-6; SiSiB® HF2038HYDROGEN TERMINATED POLYDIPHENYL SILOXANE; SiSiB® HF2068 HYDRIDETERMINATED METHYLHYDROSILOXANE DIMETHYLSILOXANE COPOLYMER 115487-49-5;SiSiB® HF2078 HYDRIDE TERMINATED POLY(PHENYLDIMETHYLSILOXY) SILOXANEPHENYL SILSESQUIOXANE, HYDROGEN-TERMINATED 68952-30-7; SiSiB® VF6060VINYLDIMETHYL TERMINATED VINYLMETHYL DIMETHYL POLYSILOXANE COPOLYMERS68083-18-1; SiSiB® VF6862 VINYLDIMETHYL TERMINATED DIMETHYL DIPHENYLPOLYSILOXANE COPOLYMER 68951-96-2; SiSiB® VF6872 VINYLDIMETHYLTERMINATED DIMETHYL-METHYLVINYL-DIPHENYL POLYSILOXANE COPOLYMER; SiSiB®PC9401 1,1,3,3-TETRAMETHYL-1,3-DIVINYLDISILOXANE 2627-95-4; SiSiB®PF1070 SILANOL TERMINATED POLYDIMETHYLSILOXANE (OF1070) 70131-67-8;SiSiB® OF1070 SILANOL TERMINATED POLYDIMETHYSILOXANE 70131-67-8;OH-ENDCAPPED POLYDIMETHYLSILOXANE HYDROXY TERMINATED OLYDIMETHYLSILOXANE73138-87-1; SiSiB® VF6030 VINYL TERMINATED POLYDIMETHYL SILOXANE68083-19-2; and, SiSiB® HF2030 HYDROGEN TERMINATED POLYDIMETHYLSILOXANEFLUID 70900-21-9.

Thus, in additional to the forgoing type of precursors, it iscontemplated that a precursor may be a compound of the following generalformula.

Wherein end cappers E₁ and E₂ are chosen from groups such as trimethylsilicon (—Si(CH₃)₃), dimethyl silicon hydroxy (—Si(CH₃)₂OH), dimethylsilicon hydride (—Si(CH₃)₂H), dimethyl vinyl silicon(—Si(CH₃)₂(CH═CH₂)), (—Si(CH₃)₂(C₆H₅)) and dimethyl alkoxy silicon(—Si(CH₃)₂(OR). The R groups R₁, R₂, R₃, and R₄ may all be different, orone or more may be the same. Thus, for example, R₂ is the same as R₃, R₃is the same as R₄, R₁ and R₂ are different with R₃ and R₄ being thesame, etc. The R groups are chosen from groups such as hydride (—H),methyl (Me)(—C), ethyl (—C—C), vinyl (—C═C), alkyl (—R)(C_(n)H_(2n+1)),allyl (—C—C═C), aryl (′R), phenyl (Ph)(—C₆H₅), methoxy (—O—C), ethoxy(—O—C—C), siloxy (—O—Si—R₃), alkoxy (—O—R), hydroxy (—O—H), phenylethyl(—C—C—C₆H₅) and methyl, phenyl-ethyl (—C—C(—C)(—C₆H₅).

In general, embodiments of formulations for polysilocarb formulationsmay for example have from about 0% to 50% MH, about 20% to about 99% MH,about 0% to about 30% siloxane backbone additives, about 1% to about 60%reactive monomers, about 30% to about 100% TV, and, about 0% to about90% reaction products of a siloxane backbone additives with a silanemodifier or an organic modifier reaction products.

In mixing the formulations sufficient time should be used to permit theprecursors to become effectively mixed and dispersed. Generally, mixingof about 15 minutes to an hour is sufficient. Typically, the precursorformulations are relatively, and essentially, shear insensitive, andthus the type of pumps or mixing are not critical. It is further notedthat in higher viscosity formulations additional mixing time may berequired. The temperature of the formulations, during mixing shouldpreferably be kept below about 45° C., and preferably about 10° C. (Itis noted that these mixing conditions are for the pre-catalyzedformulations.)

The Reaction Type Process

In the reaction type process, in general, a chemical reaction is used tocombine one, two or more precursors, typically in the presence of asolvent, to form a precursor formulation that is essentially made up ofa single polymer that can then be, catalyzed, cured and pyrolized. Thisprocess provides the ability to build custom precursor formulations thatwhen cured can provide plastics having unique and desirable featuressuch as high temperature, flame resistance and retardation, strength andother features. The cured materials can also be pyrolized to formceramics having unique features. The reaction type process allows forthe predetermined balancing of different types of functionality in theend product by selecting functional groups for incorporation into thepolymer that makes up the precursor formulation, e.g., phenyls whichtypically are not used for ceramics but have benefits for providing hightemperature capabilities for plastics, and styrene which typically doesnot provide high temperature features for plastics but provides benefitsfor ceramics.

In general a custom polymer for use as a precursor formulation is madeby reacting precursors in a condensation reaction to form the polymerprecursor formulation. This precursor formulation is then cured into apreform through a hydrolysis reaction. The condensation reaction forms apolymer of the type shown below.

Where R₁ and R₂ in the polymeric units can be a hydride (—H), a methyl(Me)(—C), an ethyl (—C—C), a vinyl (—C═C), an alkyl (—R)(C_(n)H_(2n+1)),an unsaturated alkyl (—C_(n)H_(2n−1)), a cyclic alkyl (—C_(n)H_(2n−1)),an allyl (—C—C═C), a butenyl (—C₄H₇), a pentenyl (—C₅H₉), acyclopentenyl (—C₅H₇), a methyl cyclopentenyl (—C₅H₆(CH₃)), anorbornenyl (—C_(X)H_(Y), where X=7-15 and Y=9-18), an aryl (′R), aphenyl (Ph)(—C₆H₅), a cycloheptenyl (—C₇H₁₁), a cyclooctenyl (—C₈H₁₃),an ethoxy (—O—C—C), a siloxy (—O—Si—R₃), a methoxy (—O—C), an alkoxy,(—O—R), a hydroxy, (—O—H), a phenylethyl (—C—C—C₆H₅) a methyl,phenyl-ethyl (—C—C(—C)(—C₆H₅)) and a vinylphenyl-ethyl(—C—C(C₆H₄(—C═C))). R₁ and R₂ may be the same or different. The customprecursor polymers can have several different polymeric units, e.g., A₁,A₂, A_(n), and may include as many as 10, 20 or more units, or it maycontain only a single unit, for example, MHF made by the reactionprocess may have only a single unit.

Embodiments may include precursors, which include among others, atriethoxy methyl silane, a diethoxy methyl phenyl silane, a diethoxymethyl hydride silane, a diethoxy methyl vinyl silane, a dimethyl ethoxyvinyl silane, a diethoxy dimethyl silane. an ethoxy dimethyl phenylsilane, a diethoxy dihydride silane, a triethoxy phenyl silane, adiethoxy hydride trimethyl siloxane, a diethoxy methyl trimethylsiloxane, a trimethyl ethoxy silane, a diphenyl diethoxy silane, adimethyl ethoxy hydride siloxane, and combinations and variations ofthese and other precursors, including other precursors set forth in thisspecification.

The end units, Si End 1 and Si End 2, can come from the precursors ofdimethyl ethoxy vinyl silane, ethoxy dimethyl phenyl silane, andtrimethyl ethoxy silane. Additionally, if the polymerization process isproperly controlled a hydroxy end cap can be obtained from theprecursors used to provide the repeating units of the polymer.

In general, the precursors are added to a vessel with ethanol (or othermaterial to absorb heat, e.g., to provide thermal mass), an excess ofwater, and hydrochloric acid (or other proton source). This mixture isheated until it reaches its activation energy, after which the reactiontypically is exothermic. Generally, in this reaction the water reactswith an ethoxy group of the silicon of the precursor monomer, forming ahydroxy (with ethanol as the byproduct). Once formed this hydroxybecomes subject to reaction with an ethoxy group on the silicon ofanother precursor monomer, resulting in a polymerization reaction. Thispolymerization reaction is continued until the desired chain length(s)is built.

Control factors for determining chain length, among others, are: themonomers chosen (generally, the smaller the monomers the more that canbe added before they begin to coil around and bond to themselves); theamount and point in the reaction where end cappers are introduced; andthe amount of water and the rate of addition, among others. Thus, thechain lengths can be from about 180 mw (viscosity about 5 cps) to about65,000 mw (viscosity of about 10,000 cps), greater than about 1000 mw,greater than about 10,000 mw, greater than about 50,000 mw and greater.Further, the polymerized precursor formulation may, and typically does,have polymers of different molecular weights, which can be predeterminedto provide formulation, cured, and ceramic product performance features.

Upon completion of the polymerization reaction the material istransferred into a separation apparatus, e.g., a separation funnel,which has an amount of deionized water that, for example, is from about1.2× to about 1.5× the mass of the material. This mixture is vigorouslystirred for about less than 1 minute and preferably from about 5 to 30seconds. Once stirred the material is allowed to settle and separate,which may take from about 1 to 2 hours. The polymer is the higherdensity material and is removed from the vessel. This removed polymer isthen dried by either warming in a shallow tray at 90° C. for about twohours; or, preferably, is passed through a wiped film distillationapparatus, to remove any residual water and ethanol. Alternatively,sodium bicarbonate sufficient to buffer the aqueous layer to a pH ofabout 4 to about 7 is added. It is further understood that other, andcommercial, manners of mixing, reacting and separating the polymer fromthe material may be employed.

Preferably a catalyst is used in the curing process of the polymerprecursor formulations from the reaction type process. The samepolymers, as used for curing the precursor formulations from the mixingtype process can be used. It is noted that, generally unlike the mixingtype formulations, a catalyst is not necessarily required to cure areaction type polymer. Inhibitors may also be used. However, if acatalyst is not used, reaction time and rates will be slower. The curingand the pyrolysis of the cured material from the reaction process isessentially the same as the curing and pyrolysis of the cured materialfrom the mixing process and the reaction blending process.

The reaction type process can be conducted under numerous types ofatmospheres and conditions, e.g., air, inert, N₂, Argon, flowing gas,static gas, reduced pressure, ambient pressure, elevated pressure, andcombinations and variations of these.

The Reaction Blending Type Process

In the reaction blending type process precursor are reacted to from aprecursor formulation, in the absence of a solvent.

For example, an embodiment of a reaction blending type process has aprecursor formulation that is prepared from MHF and Dicyclopentadiene(“DCPD”). Using the reactive blending process a MHF/DCPD polymer iscreated and this polymer is used as a precursor formulation. (It can beused alone to form a cured or pyrolized product, or as a precursor inthe mixing or reaction processes.) MHF of known molecular weight andhydride equivalent mass; “P01” (P01 is a 2% Pt(0)tetravinylcyclotetrasiloxane complex (e.g.,tetramethyltetravinylcyclotetrasiloxane) intetravinylcyclotetrasiloxane, diluted 20× withtetravinylcyclotetrasiloxane to 0.1% of Pt(0) complex. In this manner 10ppm Pt is provided for every 1% loading of bulk cat.) catalyst 0.20 wt %of MHF starting material (with known active equivalent weight), from 40to 90%; and Dicyclopentadiene with ≧83% purity, from 10 to 60% areutilized. In an embodiment of the process, a sealable reaction vessel,with a mixer, can be used for the reaction. The reaction is conducted inthe sealed vessel, in air; although other types of atmosphere can beutilized. Preferably, the reaction is conducted at atmospheric pressure,but higher and lower pressures can be utilized. Additionally, thereaction blending type process can be conducted under numerous types ofatmospheres and conditions, e.g., air, inert, N₂, Argon, flowing gas,static gas, reduced pressure, ambient pressure, elevated pressure, andcombinations and variations of these.

In an embodiment, 850 grams of MHF (85% of total polymer mixture) isadded to reaction vessel and heated to about 50° C. Once thistemperature is reached the heater is turned off, and 0.20% by weight P01Platinum catalyst is added to the MHF in the reaction vessel. Typically,upon addition of the catalyst bubbles will form and temp will initiallyrise approximately 2-20° C.

When the temperature begins to fall, about 150 g of DCPD (15 wt % oftotal polymer mixture) is added to the reaction vessel. The temperaturemay drop an additional amount, e.g., around 5-7° C.

At this point in the reaction process the temperature of the reactionvessel is controlled to, maintain a predetermined temperature profileover time, and to manage the temperature increase that may beaccompanied by an exotherm. Preferably, the temperature of the reactionvessel is regulated, monitored and controlled throughout the process.

In an embodiment of the MHF/DCPD embodiment of the reaction process, thetemperature profile can be as follows: let temperature reach about 80°C. (may take ˜15-40 min, depending upon the amount of materialspresent); temperature will then increase and peak at ˜104° C., as soonas temperature begins to drop, the heater set temperature is increasedto 100° C. and the temperature of the reaction mixture is monitored toensure the polymer temp stays above 80° C. for a minimum total of about2 hours and a maximum total of about 4 hours. After 2-4 hours above 80°C., the heater is turned off, and the polymer is cooled to ambient. Itbeing understood that in larger and smaller batches, continuous,semi-continuous, and other type processes the temperature and timeprofile may be different.

In larger scale, and commercial operations, batch, continuous, andcombinations of these, may be used. Industrial factory automation andcontrol systems can be utilized to control the reaction, temperatureprofiles and other processes during the reaction.

Table C sets forth various embodiments of reaction blending processes.

TABLE C degree of Equivalents Equivalents Equivalents EquivalentsEquivalents Equivalents grams/mole Material Name polymerization Si/moleO/mole H/mol Vi/mol methyl/mole C/mole MW of vinyl tetramethylcyclo- 4 44 4 0 4 4 240.51 tetrasiloxane (D₄) MHF 33 35 34 33 0 39 39 2145.345 VMF5 7 6 0 5 11 21 592.959 118.59 TV 4 4 4 0 4 4 12 344.52 86.13 VT 0200125 127 126 0 2 254 258 9451.206 4725.60 VT 0020 24 26 25 0 2 52 561965.187 982.59 VT 0080 79 81 80 0 2 162 166 6041.732 3020.87 Styrene 2104.15 52.08 Dicyclopentadiene 2 132.2 66.10 1,4-divinylbenzene 2 130.1965.10 isoprene 2 62.12 31.06 1,3 Butadiene 2 54.09 27.05 Catalyst 10 ppmPt Catalyst LP 231

In the above table, the “degree of polymerization” is the number ofmonomer units, or repeat units, that are attached together to form thepolymer. “Equivalents ______/mol” refers to the molar equivalents.“Grams/mole of vinyl” refers to the amount of a given polymer needed toprovide 1 molar equivalent of vinyl functionality. “VMH” refers tomethyl vinyl fluid, a linear vinyl material from the ethoxy process,which can be a substitute for TV. The numbers “0200” etc. for VT are theviscosity in centipoise for that particular VT.

Curing and Pyrolysis

Precursor formulations, including the polysilocarb precursorformulations from the above types of processes, as well as others, canbe cured to form a solid, semi-sold, or plastic like material.Typically, the precursor formulations are spread, shaped, or otherwiseformed into a preform, which would include any volumetric structure, orshape, including thin and thick films. In curing, the polysilocarbprecursor formulation may be processed through an initial cure, toprovide a partially cured material, which may also be referred to, forexample, as a preform, green material, or green cure (not implyinganything about the material's color). The green material may then befurther cured. Thus, one or more curing steps may be used. The materialmay be “end cured,” i.e., being cured to that point at which thematerial has the necessary physical strength and other properties forits intended purpose. The amount of curing may be to a final cure (or“hard cure”), i.e., that point at which all, or essentially all, of thechemical reaction has stopped (as measured, for example, by the absenceof reactive groups in the material, or the leveling off of the decreasein reactive groups over time). Thus, the material may be cured tovarying degrees, depending upon its intended use and purpose. Forexample, in some situations the end cure and the hard cure may be thesame. Curing conditions such as atmosphere and temperature may affectthe composition of the cured material.

In making the precursor formulation into a structure, or preform, theprecursor formulation, e.g., polysilocarb formulation, can be, forexample, formed using the following techniques: spraying, spray drying,atomization, nebulization, phase change separation, flowing, thermalspraying, drawing, dripping, forming droplets in liquid andliquid-surfactant systems, painting, molding, forming, extruding,spinning, ultrasound, vibrating, solution polymerization, emulsionpolymerization, micro-emulsion polymerization, injecting, injectionmolding, or otherwise manipulated into essentially any volumetric shape.These volumetric shapes may include for example, the following: spheres,pellets, rings, lenses, disks, panels, cones, frustoconical shapes,squares, rectangles, trusses, angles, channels, hollow sealed chambers,hollow spheres, blocks, sheets, coatings, films, skins, particulates,beams, rods, angles, slabs, columns, fibers, staple fibers, tubes, cups,pipes, and combinations and various of these and other more complexshapes, both engineering and architectural.

The forming step, the curing steps, and the pyrolysis steps may beconducted in batch processes, serially, continuously, with time delays(e.g., material is stored or held between steps), and combinations andvariations of these and other types of processing sequences. Further,the precursors can be partially cured, or the cure process can beinitiated and on going, prior to the precursor being formed into avolumetric shape. These steps, and their various combinations may be,and in some embodiments preferably are, conducted under controlled andpredetermined conditions (e.g., the material is exposed to apredetermined atmosphere, and temperature profile during the entirely ofits processing, e.g., reduced oxygen, temperature of cured preform heldat about 140° C. prior to pyrolysis). It should be further understoodthat the system, equipment, or processing steps, for forming, curing andpyrolizing may be the same equipment, continuous equipment, batch andlinked equipment, and combinations and variations of these and othertypes of industrial processes. Thus, for example, a spray dryingtechnique could form cured particles that are feed directly into afluidized bed reactor for pyrolysis.

The polysilocarb precursor formulations can be made into neat,non-reinforced, non-filled, composite, reinforced, and filledstructures, intermediates, end products, and combinations and variationsof these and other compositional types of materials. Further, thesestructures, intermediates and end products can be cured (e.g., greencured, end cured, or hard cured), uncured, pyrolized to a ceramic, andcombinations and variations of these (e.g., a cured material may befilled with pyrolized material derived from the same polysilocarb as thecured material).

The precursor formulations may be used to form a “neat” material, (by“neat” material it is meant that all, and essentially all of thestructure is made from the precursor material or unfilled formulation;and thus, there are no fillers or reinforcements).

The polysilocarb precursor formulations may be used to coat orimpregnate a woven or non-woven fabric, made from for example carbonfiber, glass fibers or fibers made from a polysilocarb precursorformulation (the same or different formulation), to from a prepregmaterial. Thus, the polysilocarb precursor formulations may be used toform composite materials, e.g., reinforced products. For example, theformulation may be flowed into, impregnated into, absorbed by orotherwise combined with a reinforcing material, such as carbon fibers,glass fiber, woven fabric, grapheme, carbon nanotubes, thin films,precipitates, sand, non-woven fabric, copped fibers, fibers, rope,braided structures, ceramic powders, glass powders, carbon powders,graphite powders, ceramic fibers, metal powders, carbide pellets orcomponents, staple fibers, tow, nanostructures of the above, polymerderived ceramics, any other material that meets the temperaturerequirements of the process and end product, and combinations andvariations of these. The reinforcing material may also be made from, orderived from the same material as the formulation that has been formedinto a fiber and pyrolized into a ceramic, or it may be made from adifferent precursor formulation material, which has been formed into afiber and pyrolized into a ceramic.

The polysilocarb precursor formulation may be used to form a filledmaterial. A filled material would be any material having other solid, orsemi-solid, materials added to the polysilocarb precursor formulation.The filler material may be selected to provide certain features to thecured product, the ceramic product and both. These features may relateto, or be, for example, aesthetic, tactile, thermal, density, radiation,chemical, cost, magnetic, electric, and combinations and variations ofthese and other features. These features may be in addition to strength.Thus, the filler material may not affect the strength of the cured orceramic material, it may add strength, or could even reduce strength insome situations. The filler material could impart color, magneticcapabilities, fire resistances, flame retardance, heat resistance,electrical conductivity, anti-static, optical properties (e.g.,reflectivity, refractivity and iridescence), aesthetic properties (suchas stone like appearance in building products), chemical resistivity,corrosion resistance, wear resistance, reduced cost, abrasionsresistance, thermal insulation, UV stability, UV protective, and otherfeatures that may be desirable, necessary, and both, in the end productor material. Thus, filler materials could include carbon black, copperlead wires, thermal conductive fillers, electrically conductive fillers,lead, optical fibers, ceramic colorants, pigments, oxides, sand, dyes,powders, ceramic fines, polymer derived ceramic particles, pore-formers,carbosilanes, silanes, silazanes, silicon carbide, carbosilazanes,siloxane, powders, ceramic powders, metals, metal complexes, carbon,tow, fibers, staple fibers, boron containing materials, milled fibers,glass, glass fiber, fiber glass, and nanostructures (includingnanostructures of the forgoing) to name a few.

The polysilocarb formulation and products derived or made from thatformulation may have metals and metal complexes. Filled materials wouldinclude reinforced materials. In many cases, cured, as well as pyrolizedpolysilocarb filled materials can be viewed as composite materials.Generally, under this view, the polysilocarb would constitute the bulkor matrix phase, (e.g., a continuous, or substantially continuousphase), and the filler would constitute the dispersed (e.g.,non-continuous), phase. Depending upon the particular application,product or end use, the filler can be evenly distributed in theprecursor formulation, unevenly distributed, distributed over apredetermined and controlled distribution gradient (such as from apredetermined rate of settling), and can have different amounts indifferent formulations, which can then be formed into a product having apredetermined amounts of filler in predetermined areas (e.g., striatedlayers having different filler concentration). It should be noted,however, that by referring to a material as “filled” or “reinforced” itdoes not imply that the majority (either by weight, volume, or both) ofthat material is the polysilcocarb. Thus, generally, the ratio (eitherweight or volume) of polysilocarb to filler material could be from about0.1:99.9 to 99.9:0.1.

The polysilocarb precursor formulations may be used to formnon-reinforced materials, which are materials that are made ofprimarily, essentially, and preferably only from the precursormaterials; but may also include formulations having fillers or additivesthat do not impart strength.

The curing may be done at standard ambient temperature and pressure(“SATP”, 1 atmosphere, 25° C.), at temperatures above or below thattemperature, at pressures above or below that pressure, and over varyingtime periods. The curing can be conducted over various heatings, rate ofheating, and temperature profiles (e.g., hold times and temperatures,continuous temperature change, cycled temperature change, e.g., heatingfollowed by maintaining, cooling, reheating, etc.). The time for thecuring can be from a few seconds (e.g., less than about 1 second, lessthan 5 seconds), to less than a minute, to minutes, to hours, to days(or potentially longer). The curing may also be conducted in any type ofsurrounding environment, including for example, gas, liquid, air, water,surfactant containing liquid, inert atmospheres, N₂, Argon, flowing gas(e.g., sweep gas), static gas, reduced O₂, reduced pressure, elevatedpressure, ambient pressure, controlled partial pressure and combinationsand variations of these and other processing conditions. For high puritymaterials, the furnace, containers, handling equipment, atmosphere, andother components of the curing apparatus and process are clean,essentially free from, and do not contribute any elements or materials,that would be considered impurities or contaminants, to the curedmaterial. In an embodiment, the curing environment, e.g., the furnace,the atmosphere, the container and combinations and variations of thesecan have materials that contribute to or effect, for example, thecomposition, catalysis, stoichiometry, features, performance andcombinations and variations of these in the preform, the ceramic and thefinal applications or products.

Preferably, in embodiments of the curing process, the curing takes placeat temperatures in the range of from about 5° C. or more, from about 20°C. to about 250° C., from about 20° C. to about 150° C., from about 75°C. to about 125° C., and from about 80° C. to 90° C. Although higher andlower temperatures and various heating profiles, (e.g., rate oftemperature change over time (“ramp rate”, e.g., Δ degrees/time), holdtimes, and temperatures) can be utilized.

The cure conditions, e.g., temperature, time, ramp rate, may bedependent upon, and in some embodiments can be predetermined, in wholeor in part, by the formulation to match, for example the size of thepreform, the shape of the preform, or the mold holding the preform toprevent stress cracking, off gassing, or other phenomena associated withthe curing process. Further, the curing conditions may be such as totake advantage of, preferably in a controlled manner, what may havepreviously been perceived as problems associated with the curingprocess. Thus, for example, off gassing may be used to create a foammaterial having either open or closed structure. Similarly, curingconditions can be used to create or control the microstructure and thenanostructure of the material. In general, the curing conditions can beused to affect, control or modify the kinetics and thermodynamics of theprocess, which can affect morphology, performance, features andfunctions, among other things.

Upon curing the polysilocarb precursor formulation a cross linkingreaction takes place that provides in some embodiments a cross-linkedstructure having, among other things, an —R₁—Si—C—C—Si—O—Si—C—C—Si—R₂—where R₁ and R₂ vary depending upon, and are based upon, the precursorsused in the formulation. In an embodiment of the cured materials theymay have a cross-linked structure having 3-coordinated silicon centersto another silicon atom, being separated by fewer than 5 atoms betweensilicons.

During the curing process some formulations may exhibit an exotherm,i.e., a self heating reaction, that can produce a small amount of heatto assist or drive the curing reaction, or that may produce a largeamount of heat that may need to be managed and removed in order to avoidproblems, such as stress fractures. During the cure off gassingtypically occurs and results in a loss of material, which loss isdefined generally by the amount of material remaining, e.g., cure yield.Embodiments of the formulations, cure conditions, and polysilocarbprecursor formulations of embodiments of the present inventions can havecure yields of at least about 90%, about 92%, about 100%. In fact, withair cures the materials may have cure yields above 100%, e.g., about101-105%, as a result of oxygen being absorbed from the air.Additionally, during curing the material typically shrinks, thisshrinkage may be, depending upon the formulation, cure conditions, andthe nature of the preform shape, and whether the preform is reinforced,filled, neat or unreinforced, from about 20%, less than 20%, less thanabout 15%, less than about 5%, less than about 1%, less than about 0.5%,less than about 0.25% and smaller.

Curing of the preform may be accomplished by any type of heatingapparatus, or mechanisms, techniques, or morphologies that has therequisite level of temperature and environmental control, for example,heated water baths, electric furnaces, microwaves, gas furnaces,furnaces, forced heated air, towers, spray drying, falling filmreactors, fluidized bed reactors, lasers, indirect heating elements,direct heating, infrared heating, UV irradiation, RF furnace, in-situduring emulsification via high shear mixing, in-situ duringemulsification via ultrasonication.

The cured preforms, either unreinforced, neat, filled or reinforced, maybe used as a stand alone product, an end product, a final product, or apreliminary product for which later machining or processing may beperformed on. The preforms may also be subject to pyrolysis, whichconverts the preform material into a ceramic.

In pyrolizing the preform, or cured structure, or cured material, it isheated to about 600° C. to about 2,300° C.; from about 650° C. to about1,200° C., from about 800° C. to about 1300° C., from about 900° C. toabout 1200° C. and from about 950° C. to 1150° C. At these temperaturestypically all organic structures are either removed or combined with theinorganic constituents to form a ceramic. Typically at temperatures inthe about 650° C. to 1,200° C. range the resulting material is anamorphous glassy ceramic. When heated above about 1,200° C. the materialtypically may from nano crystalline structures, or micro crystallinestructures, such as SiC, Si3N₄, SiCN, β SiC, and above 1,900° C. an αSiC structure may form, and at and above 2,200° C. α SiC is typicallyformed. The pyrolized, e.g., ceramic materials can be single crystal,polycrystalline, amorphous, and combinations, variations and subgroupsof these and other types of morphologies.

The pyrolysis may be conducted under many different heating andenvironmental conditions, which preferably include thermo control,kinetic control and combinations and variations of these, among otherthings. For example, the pyrolysis may have various heating ramp rates,heating cycles and environmental conditions. In some embodiments, thetemperature may be raised, and held a predetermined temperature, toassist with known transitions (e.g., gassing, volatilization, molecularrearrangements, etc.) and then elevated to the next hold temperaturecorresponding to the next known transition. The pyrolysis may take placein reducing atmospheres, oxidative atmospheres, low O₂, gas rich (e.g.,within or directly adjacent to a flame), inert, N₂, Argon, air, reducedpressure, ambient pressure, elevated pressure, flowing gas (e.g., sweepgas, having a flow rate for example of from about from about 15.0 GHSVto about 0.1 GHSV, from about 6.3 GHSV to about 3.1 GHSV, and at about3.9 GHSV), static gas, and combinations and variations of these.

The pyrolysis is conducted over a time period that preferably results inthe complete pyrolysis of the preform. For high purity materials, thefurnace, containers, handling equipment, and other components of thepyrolysis apparatus are clean, essentially free from, free from and donot contribute any elements or materials, that would be consideredimpurities or contaminants, to the pyrolized material. A constant flowrate of “sweeping” gas can help purge the furnace during volatilegeneration. In an embodiment, the pyrolysis environment, e.g., thefurnace, the atmosphere, the container and combinations and variationsof these, can have materials that contribute to or effect, for example,the composition, stoichiometry, features, performance and combinationsand variations of these in the ceramic and the final applications orproducts.

During pyrolysis material may be lost through off gassing. The amount ofmaterial remaining at the end of a pyrolysis step, or cycle, is referredto as char yield (or pyrolysis yield). The formulations and polysilocarbprecursor formulations of embodiments of the present formulations canhave char yields for SiOC formation of at least about 60%, about 70%,about 80%, and at least about 90%, at least about 91% and greater. Infact, with air pyrolysis the materials may have char yields well above91%, which can approach 100%. In order to avoid the degradation of thematerial in an air pyrolysis (noting that typically pyrolysis isconducted in inert atmospheres, reduced oxygen atmosphere, essentiallyinert atmosphere, minimal oxygen atmospheres, and combinations andvariations of these) specifically tailored formulations can be used. Forexample, formulations high in phenyl content (at least about 11%, andpreferably at least about 20% by weight phenyls), formulations high inallyl content (at least about 15% to about 60%) can be used for airpyrolysis to mitigate the degradation of the material.

The initial or first pyrolysis step for SiOC formation, in someembodiments and for some uses, generally yields a structure that is notvery dense, and for example, may not reached the density required forits intended use. However, in some examples, such as the use oflightweight spheres, proppants, pigments, and others, the firstpyrolysis may be, and is typically sufficient. Thus, generally areinfiltration process may be performed on the pyrolized material, toadd in additional polysilocarb precursor formulation material, to fillin, or fill, the voids and spaces in the structure. This reinfiltratedmaterial may then be cured and repyrolized. (In some embodiments, thereinfiltrated materials is cured, but not pyrolized.) This process ofpyrolization, reinfiltration may be repeated, through one, two, three,and up to 10 or more times to obtain the desired density of the finalproduct.

In some embodiments, upon pyrolization, graphenic, graphitic, amorphouscarbon structures and combinations and variations of these are presentin the Si—O—C ceramic. A distribution of silicon species, consisting ofSiOxCy structures, which result in SiO4, SiO3C, SiO2C2, SiOC3, and SiC4are formed in varying ratios, arising from the precursor choice andtheir processing history. Carbon is generally bound between neighboringcarbons and/or to a Silicon atom. In general, in the ceramic state,carbon is largely not coordinated to an oxygen atom, thus oxygen islargely coordinated to silicon

The pyrolysis may be conducted in any heating apparatus that maintainsthe request temperature and environmental controls. Thus, for examplepyrolysis may be done with gas fired furnaces, electric furnaces, directheating, indirect heating, fluidized beds, kilns, tunnel kilns, boxkilns, shuttle kilns, coking type apparatus, lasers, microwaves, andcombinations and variations of these and other heating apparatus andsystems that can obtain the request temperatures for pyrolysis.

Custom and predetermined control of when chemical reactions,arrangements and rearrangements, occur in the various stages of theprocess from raw material to final end product can provide for reducedcosts, increased process control, increased reliability, increasedefficiency, enhanced product features, increased purity, andcombinations and variation of these and other benefits. The sequencingof when these transformations take place can be based upon theprocessing or making of precursors, and the processing or making ofprecursor formulations; and may also be based upon cure and pyrolysisconditions. Further, the custom and predetermined selection of thesesteps, formulations and conditions, can provide enhanced product andprocessing features through the various transformations, e.g., chemicalreactions; molecular arrangements and rearrangements; and microstructurearrangements and rearrangements.

At various points during the manufacturing process, the polymer derivedceramic structures, e.g., polysilocarb structures, intermediates and endproducts, and combinations and variations of these, may be machined,milled, molded, shaped, drilled, etched, or otherwise mechanicallyprocessed and shaped.

Starting materials, precursor formulations, polysilocarb precursorformulations, as well as, methods of formulating, making, forming,curing and pyrolizing, precursor materials to form polymer derivedmaterials, structures and ceramics, are set forth in Published US PatentApplications, Publication Nos. 2014/0343220, 2014/0274658, and2014/0326453, and U.S. Patent Applications Ser. Nos. 61/946,598,62/055,397 and 62/106,094, the entire disclosures of each of which areincorporated herein by reference.

In preferred embodiments of the polysilocarb derived ceramic pigmentsthe amounts of Si, O, C for the total amount of pigment are set forth inthe Table 4.

TABLE 4 Si O C Lo Hi Lo Hi Lo Hi Wt % 35.00% 50.00% 10.00% 35.00% 5.00%30.00% Mole Ratio 1.000 1.429 0.502 1.755 0.334 2.004 Mole % 15.358%63.095% 8.821% 56.819% 6.339% 57.170%

In general, embodiments of the pyrolized ceramic polysilocarb pigmentscan have about 30% to about 60% Si, can have about 5% to about 40% O,and can have about 3% to about 35% carbon. Greater and lesser amountsare also contemplated.

The type of carbon present in preferred embodiments of the polysilocarbderived ceramic pigments can be free carbon, (e.g., turbostratic,amorphous, graphenic, graphitic forms of carbon) and Carbon that isbound to Silicon. Embodiments having preferred amounts of free carbonand Silicon-bound-Carbon (Si—C) are set forth in Table 5.

TABLE 5 Embodiment % Free Carbon % Si—C type 1 64.86 35.14 2 63.16 36.853 67.02 32.98 4 58.59 41.41 5 65.70 31.66 6 62.72 30.82 7 61.68 34.44 869.25 27.26 9 60.00 27.54

Generally, embodiments of polysilocarb derived ceramic pigments can havefrom about 20% free carbon to about 80% free carbon, and from about 20%Si—C bonded carbon to about 80% Si—C bonded carbon. Greater and lesseramounts are also contemplated.

Typically, embodiments of the pyrolized ceramic polysilocarb pigmentscan have other elements present, such as Nitrogen and Hydrogen.Embodiments can have the amounts of these other materials as set out inTable 6. (Note that these are typical for embodiments of net materials.If fillers, additives, or other materials are combined with or into theprecursor formulation; then such materials can generally be present to agreater or lesser extent in the pyrolized ceramic material)

TABLE 6 H N Lo Hi Lo Hi Wt % 0.00% 2.20% 0% 2% Mole Ratio 0.000 1.751 0 0.1 Mole % 0.000% 48.827% 0% 3%

The polysilocarb derived ceramic pigments can exhibit sparkle, andimpart sparkle to a coating. The degree and effect of sparkle can bepredetermined by such factors as for example the surface exposure duringpyrolysis, heat profile, and the type of gas (nitrogen, argon etc.) usedduring pyrolysis.

EXAMPLES

The following examples are provided to illustrate various embodimentsof, among other things, precursor formulations, processes, methods,apparatus, articles, compositions, and applications of the presentinventions. These examples are for illustrative purposes, and should notbe viewed as, and do not otherwise limit the scope of the presentinventions. The percentages used, unless specified otherwise, are weightpercent of the total batch, pigment, formulation or structure.

Example 1

A polymer derived ceramic black pigment having 41% Si, 31% O, and 27% C(with 27.5% of the carbon being the Si—C bonded type, and the remainingcarbon being the graphitic type) has the following properties.

Physical and Chemical Properties Particle Size (D50) capabilities 1-150μm Specific Gravity 2.10 Bulk Density, lbs/ft³ 78 g/cc 1.25 MorphologyAngular - Fragmented Solubility in 12/3 HCL/HF Acid 0.4 (% weight loss)

Masstone (typical) 800 series DFT (mil/μ) 0.8/20 Gloss 20° 74.6 Gloss60° 97.4 Color Development* L* 4.64 a* 0.25 B* 0.95 *commercialautomotive binder system.

Weather test 500 hr. Chalking none Blistering none Whitening none ColorDevelopment* L (init./final) 4.64/4.51 a (init./final) 0.25/0.17 b(init./final) 0.95/0.97 Gloss Retention 98.4% *QUV per ASTM G154.

Environmental properties Salt Spray (500 hrs.) Pass Conductivity (δ)<10⁻³ Scratch resistance (ISO 1518 stylus) To 5 Kg weight No cut (pass)Pencil Hardness HB

Example 2

A polymer derived ceramic black pigment having 45% Si, 22% O, and 33% C(with 34.4% of the carbon being the Si—C bonded type, and the remainingcarbon being the graphitic type) and an agglomerate size of 10 μm and aparticle size of 0.1 μm.

Example 3

A polymer derived ceramic black pigment having 44% Si, 31% O, and 25% C(with 27.3% of the carbon being the Si—C bonded type, and the remainingcarbon being the graphitic type) and an agglomerate size of 15 μm and aparticle size of 1 μm.

Example 4

A polymer derived ceramic black pigment having 50% Si, 20% O, and 30% C(with 25% of the carbon being the Si—C bonded type, and the remainingcarbon being the graphitic type) and an agglomerate size of 10 μm and aparticle size of 0.5 μm.

Example 5

A polysilocarb batch having 75% MH, 15% TV, 10% VT and 1% catalyst (10ppm platinum and 0.5% Luperox 231 peroxide) is cured and pyrolized toform black ceramic pigment.

Example 6

A polysilocarb batch having 70% MH, 20% TV, 10% VT and 1% catalyst (10ppm platinum and 0.5% Luperox 231 peroxide) is cured and pyrolized toform black ceramic pigment.

Example 7

A polysilocarb batch having 50% by volume carbon black is added to apolysilocarb batch having 70% MH, 20% TV, 10% VT and 1% catalyst (10 ppmplatinum and 0.5% Luperox 231 peroxide) is cured and pyrolized to formblack ceramic filled pigment.

Example 8

A polysilocarb batch having 70% of the MH precursor (molecular weight ofabout 800) and 30% of the TV precursor is cured and pyrolized to formblack ceramic pigment.

Example 9

A polysilocarb batch having 10% of the MH precursor (molecular weight ofabout 800), 73% of the methyl terminated phenylethyl polysiloxaneprecursor (molecular weight of about 1,000), and 16% of the TVprecursor, and 1% of the OH terminated is cured and pyrolized to formblack ceramic pigment.

Example 10

A polysilocarb reaction blend batch having 85/15 MHF/DCPD is cured andpyrolized in a single heating step in a gas rich furnace at 1,100° C. toform black ceramic pigment.

Example 11

A polysilocarb reaction blend batch having 85/15 MHF/DCPD with 1% P01catalyst and 1% peroxide catalyst is cured at 100° C. in a reducedoxygen atmosphere and the cure material is then pyrolized in a reducedpressure argon flowing environment at 1,200° C. to form black ceramicpigment.

Example 12

A polysilocarb reaction blend batch having 85/15 MHF/DCPD with 1% P01catalyst and 3% TV (which functions as a curie rate accelerator) iscured and pyrolized to form a black ceramic pigment.

Example 13

A polysilocarb reaction blend batch having 65/35 MHF/DCPD is cured andpyrolized to form a black ceramic pigment.

Example 14

A polysilocarb reaction blend batch having 70/30 MHF/DCPD is cured andpyrolized to form a black ceramic pigment.

Example 15

A polysilocarb reaction blend batch having 60/40 MHF/DCPD is cured andpyrolized to form a black ceramic pigment.

Example 16

A polysilocarb batch having 50-65% MHF; 5-10% Tetravinyl; and 25-40%Diene (Diene=Dicyclopentadiene or Isoprene or Butadiene), preferablycatalyzed with P01 or other Platinum catalyst is cured and pyrolized toform a black ceramic pigment.

Example 17

A polysilocarb batch having 60-80% MHF and 20-40% Isoprene, preferablycatalyzed with P01 or other Platinum catalyst is cured and pyrolized toform a black ceramic pigment.

Example 18

A polysilocarb batch having 50-65% MHF and 35-50% Tetravinyl, preferablycatalyzed with P01 or other Platinum catalyst is cured and pyrolized toform a black ceramic pigment.

Example 19

A polysilocarb reaction blend batch having 85/15 MHF/DCPD, andpreferably using P01 and Luperox® 231 catalysts is cured and pyrolizedto form a black ceramic pigment.

Example 20

A polysilocarb reaction blend batch having 65/35 MHF/DCPD, andpreferably using P01 and Luperox® 231 catalysts is cured and pyrolizedto form a black ceramic pigment.

Example 21

A polysilocarb batch having 46% MHF and 34% TV and 20 VT, with P01catalyst is cured and pyrolized to form a black ceramic pigment.

Example 22

A polysilocarb reaction blend batch having 50/50 MHF/DCPD with 4% TV and5 ppm Pt catalyst is cured and pyrolized to form a black ceramicpigment.

Example 23

Using the reaction type process a precursor formulation was made usingthe following formulation. The temperature of the reaction wasmaintained at 61° C. for 21 hours.

Moles of % of Total % of Reactant/ Moles of Moles Moles Reactant orSolvent Mass Total MW solvent Silane of Si of EtOH Methyltriethoxysilane(FIG. 37) 120.00 19.5% 178.30 0.67 47.43% 0.67 2.02Phenylmethyldiethoxysilane (FIG. 38) 0.00 0.0% 210.35 — 0.00% — —Dimethyldiethoxysilane (FIG. 42) 70.00 11.4% 148.28 0.47 33.27% 0.470.94 Methyldiethoxysilane (FIG. 39) 20.00 3.3% 134.25 0.15 10.50% 0.150.30 Vinylmethyldiethoxysilane (FIG. 40) 20.00 3.3% 160.29 0.12 8.79%0.12 0.25 Trimethyethoxysilane (FIG. 48) 0.00 0.0% 118.25 — 0.00% — —Hexane in hydrolyzer 0.00 0.0% 86.18 — Acetone in hydrolyzer 320.0052.0% 58.08 5.51 Ethanol in hydrolyzer 0.00 0.0% 46.07 — Water inhydrolyzer 64.00 10.4% 18.00 3.56 HCl 0.36 0.1% 36.00 0.01 Sodiumbicarbonate 0.84 0.1% 84.00 0.01

Is cured and pyrolized to form a black ceramic pigment.

Example 24

Using the reaction type process a precursor formulation was made usingthe following formulation. The temperature of the reaction wasmaintained at 72° C. for 21 hours.

Moles of % of Total % of Reactant/ Moles of Moles Moles Reactant orSolvent Mass Total MW solvent Silane of Si of EtOH Phenyltriethoxysilane(FIG. 45) 234.00 32.0% 240.37 0.97 54.34% 0.97 2.92Phenylmethyldiethoxysilane (FIG. 38) 90.00 12.3% 210.35 0.43 23.88% 0.430.86 Dimethyldiethoxysilane (FIG. 42) 0.00 0.0% 148.28 — 0.00% — —Methyldiethoxysilane (FIG. 39) 28.50 3.9% 134.25 0.21 11.85% 0.21 0.42Vinylmethyldiethoxysilane (FIG. 40) 28.50 3.9% 160.29 0.18 9.93% 0.180.36 Trimethyethoxysilane (FIG. 48) 0.00 0.0% 118.25 — 0.00% — — Acetonein hydrolyzer 0.00 0.0% 58.08 — Ethanol in hydrolyzer 265.00 36.3% 46.075.75 Water in hydrolyzer 83.00 11.4% 18.00 4.61 HCl 0.36 0.0% 36.00 0.01Sodium bicarbonate 0.84 0.1% 84.00 0.01

Is cured and pyrolized to form a black ceramic pigment.

Example 25

Using the reaction type process a precursor formulation was made usingthe following formulation. The temperature of the reaction wasmaintained at 61° C. for 21 hours.

Moles of % of Total % of Reactant/ Moles of Moles Moles Reactant orSolvent Mass Total MW solvent Silane of Si of EtOH Phenyltriethoxysilane(FIG. 45) 142.00 21.1% 240.37 0.59 37.84% 0.59 1.77Phenylmethyldiethoxysilane (FIG. 38) 135.00 20.1% 210.35 0.64 41.11%0.64 1.28 Dimethyldiethoxysilane (FIG. 42) 0.00 0.0% 148.28 — 0.00% — —Methyldiethoxysilane (FIG. 39) 24.00 3.6% 134.25 0.18 11.45% 0.18 0.36Vinylmethyldiethoxysilane (FIG. 40) 24.00 3.6% 160.29 0.15 9.59% 0.150.30 Trimethyethoxysilane (FIG. 48) 0.00 0.0% 118.25 — 0.00% — — Acetonein hydrolyzer 278.00 41.3% 58.08 4.79 Ethanol in hydrolyzer 0.00 0.0%46.07 — Water in hydrolyzer 69.00 10.2% 18.00 3.83 HCl 0.36 0.1% 36.000.01 Sodium bicarbonate 0.84 0.1% 84.00 0.01

Is cured and pyrolized to form a black ceramic pigment.

Example 26

Using the reaction type process a precursor formulation was made usingthe following formulation. The temperature of the reaction wasmaintained at 72° C. for 21 hours.

Moles of % of Total % of Reactant/ Moles of Moles Moles Reactant orSolvent Mass Total MW solvent Silane of Si of EtOH Methyltriethoxysilane(FIG. 37) 0.00 0.0% 178.30 — 0.00% — — Phenylmethyldiethoxysilane (FIG.38) 0.00 0.0% 210.35 — 0.00% — — Dimethyldiethoxysilane (FIG. 42) 567.2% 148.28 0.38 17.71% 0.38 0.76 Methyldiethoxysilane (FIG. 39) 18223.2% 134.25 1.36 63.57% 1.36 2.71 Vinylmethyldiethoxysilane (FIG. 40)64 8.2% 160.29 0.40 18.72% 0.40 0.80 Triethoxysilane (FIG. 44) 0.00 0.0%164.27 — 0.00% — — Hexane in hydrolyzer 0.00 0.0% 86.18 — Acetone inhydrolyzer 0.00 0.0% 58.08 — Ethanol in hydrolyzer 400.00 51.1% 46.078.68 Water in hydrolyzer 80.00 10.2% 18.00 4.44 HCl 0.36 0.0% 36.00 0.01Sodium bicarbonate 0.84 0.1% 84.00 0.01

Is cured and pyrolized to form a black ceramic pigment.

Example 27

Using the reaction type process a precursor formulation was made usingthe following formulation. The temperature of the reaction wasmaintained at 61° C. for 21 hours.

Moles of % of Total % of Reactant/ Moles of Moles Moles Reactant orSolvent Mass Total MW solvent Silane of Si of EtOH Phenyltriethoxysilane(FIG. 45) 198.00 26.6% 240.37 0.82 52.84% 0.82 2.47Phenylmethyldiethoxysilane (FIG. 38) 0.00 0.0% 210.35 — 0.00% — —Dimethyldiethoxysilane (FIG. 42) 109.00 14.6% 148.28 0.74 47.16% 0.741.47 Methyldiethoxysilane (FIG. 39) 0.00 0.0% 134.25 — 0.00% — —Vinylmethyldiethoxysilane (FIG. 40) 0.00 0.0% 160.29 — 0.00% — —Trimethyethoxysilane (FIG. 48) 0.00 0.0% 118.25 — 0.00% — — Acetone inhydrolyzer 365.00 49.0% 58.08 6.28 Ethanol in hydrolyzer 0.00 0.0% 46.07— Water in hydrolyzer 72.00 9.7% 18.00 4.00 HCl 0.36 0.0% 36.00 0.01Sodium bicarbonate 0.84 0.1% 84.00 0.01

Is cured and pyrolized to form a black ceramic pigment.

Example 28

Using the reaction type process a precursor formulation was made usingthe following formulation. The temperature of the reaction wasmaintained at 72° C. for 21 hours.

Moles of % of Total % of Reactant/ Moles of Moles Moles Reactant orSolvent Mass Total MW solvent Silane of Si of EtOH Phenyltriethoxysilane(FIG. 45) 180.00 22.7% 240.37 0.75 44.10% 0.75 2.25Phenylmethyldiethoxysilane (FIG. 38) 50.00 6.3% 210.35 0.24 14.00% 0.240.48 Dimethyldiethoxysilane (FIG. 42) 40.00 5.0% 148.28 0.27 15.89% 0.270.54 Methyldiethoxysilane (FIG. 39) 30.00 3.8% 134.25 0.22 13.16% 0.220.45 Vinyl methyldiethoxysilane (FIG. 40) 35.00 4.4% 160.29 0.22 12.86%0.22 0.44 Trimethyethoxysilane (FIG. 48) 0.00 0.0% 118.25 — 0.00% — —Hexane in hydrolyzer 0.00 0.0% 86.18 — Acetone in hydrolyzer 0.00 0.0%58.08 — Ethanol in hydrolyzer 380.00 48.0% 46.07 8.25 Water inhydrolyzer 76.00 9.6% 18.00 4.22 HCl 0.36 0.0% 36.00 0.01 Sodiumbicarbonate 0.84 0.1% 84.00 0.01

Is cured and pyrolized to form a black ceramic pigment.

Example 29

A polysilocarb formulation has 95% MHF and 5% TV is cured and pyrolizedto form a black ceramic pigment.

Example 30

A polysilocarb formulation has 90% MHF, 5% TV, and 5% VT is cured andpyrolized to form a black ceramic pigment.

Example 31

A polysilocarb formulation has 0-20% MHF, 0-30% TV, 50-100% H62 C and0-5% a hydroxy terminated dimethyl polysiloxane is cured and pyrolizedto form a black ceramic pigment.

Example 32

Mill bases using the pigment of Examples 1, 2, 8, 10 and 12 are made.The mill bases have a thermoplastic acrylic polyol resin, a solventMethyl amyl ketone and has a pigment loading of 1.5 to 6.0 pounds pergallon. The mill bases exhibits Newtonian flow characteristics.

Example 33

Mill bases using the pigment of Examples 2-4, 5, 6, 11, and 13 are made.The mill bases have a thermoplastic acrylic polyol resin, a solventMethyl Amyl ketone and has a pigment loading of 1.5 to 6.0pounds/gallon. The mill bases exhibits Newtonian flow characteristics.

Example 34

Mill bases using the pigment of Examples 1, 13, 14, 16 and 23 are made.The mill bases have a thermoplastic acrylic polyol resin, a solventmethyl amyl ketone and has a pigment loading of 1.5 to 6.0 pounds pergallon. The mill bases exhibits Newtonian flow characteristics.

Example 35

A mill base using any of the pigments of Examples 1 to 31 is made. Themill base has a thermoplastic acrylic polyol resin, a solvent methylamyl ketone and has a pigment loading of 1.5 to 6.0 pounds/gallon.

Example 36

Mill bases using the pigment of Examples 1, 2, 8, 10 and 12 are made.The mill bases have a thermoplastic acrylic emulsion, a solvent waterand has a pigment loading of 1.5 to 6 pounds/gallon

Example 37

Mill bases using the pigment of Examples 1, 2, 8, 10 and 12 are made.The mill bases have a low molecular weight Bisphenol A diglycidal etherresin, a solvent xylene, and has a pigment loading of 1.5 to 6.0pounds/gallon

Example 38

Mill bases using the pigment of Examples 1, 2, 8, 10 and 12 are made.The mill bases have a modified hydroxyl ethyl cellulose, surfactant, andwater and has a pigment loading of 1.5 to 8.0 pounds/gallon

Example 39

Mill bases using the pigment of Examples 1, 2, 8, 10 and 12 are made.The mill bases have a silicone resin, a solvent xylene and has a pigmentloading of 1.5 to 5.0 pounds/gallon

Example 40

Mill bases using the pigment of Examples 1, 2, 8, 10 and 12 are made.The mill bases have a mineral oil based resin, a solvent mineral spiritsand has a pigment loading of 1.5 to 8 pounds/gallon.

Example 41

Mill bases using the pigment of Examples 1, 2, 8, 10 and 12 are made.The mill bases have a mineral oil based resin, a solvent mineral spiritsand has a pigment loading of 2 pounds/gallon.

Example 42

Black polysilocarb derived ceramic pigment is loaded at 1 g/Kg of athermoplastic acrylic resin having the composition of S/MMA/BA/HEA(where S is styrene, MMA is methyl methacrylate, BA is n-butyl acrylate,and HEA is 2-hydroxyethyl acrylate). The resin has a weight ratio forS:MMA:BA:HEA of 15:14:40:30.

Example 43

Black polysilocarb derived ceramic pigment is loaded at 30 g/Kg of athermoplastic acrylic resin having the composition of S/MMA/BA/HEA(where S is styrene, MMA is methyl methacrylate, BA is n-butyl acrylate,and HEA is 2-hydroxyethyl acrylate). The resin has a weight ratio forS:MMA:BA:HEA of 15:14:40:30.

Example 44

Black polysilocarb derived ceramic pigment is loaded at 100 g/Kg of athermoplastic acrylic resin having the composition of S/MMA/BA/HEA(where S is styrene, MMA is methyl methacrylate, BA is n-butyl acrylate,and HEA is 2-hydroxyethyl acrylate). The resin has a weight ratio forS:MMA:BA:HEA of 15:14:40:30.

Example 45

Black polysilocarb derived ceramic pigments of Example 1-6, 8 10, and 12are loaded at 6 pounds/gallon of a water-reducible acrylic resin havingthe composition of MMA/BA/HEMA/AA (where HEMA is 2-hydroxyethylmethacrylate, and AA is acrylic acid). The resin has a weight ratio forMMA:BA:HEMA:AA of 60:22.2:10:7.8.

Example 46

Black polysilocarb derived ceramic pigment is loaded at 5 pounds/gallonof a water-reducible acrylic resin having the composition ofMMA/BA/HEMA/AA (where HEMA is 2-hydroxyethyl methacrylate, and AA isacrylic acid). The resin has a weight ratio for MMA:BA:HEMA:AA of60:22.2:10:7.8.

Example 47

Black polysilocarb derived ceramic pigments of Example 1-31 are loadedat 1.5 to 8 pounds/gallon of a water-reducible acrylic resin having thecomposition of MMA/BA/HEMA/AA (where HEMA is 2-hydroxyethylmethacrylate, and AA is acrylic acid). The resin has a weight ratio forMMA:BA:HEMA:AA of 60:22.2:10:7.8.

Example 48

A very high temperature coating (VHTC) having a silicon based resin andhaving polysilocarb ceramic pigment, size 0.25 μm, and a loading of 0.3lbs/gal (23.97 g/L) has the following characteristics Good hiding power,excellent heat stability, jet black masstone, excellent UV stability andoutdoor weather resistance, excellent humidity resistance, excellentcorrosion resistance and hardness.

Example 49

A very high temperature coating having a silicon based resin and havingpolysilocarb ceramic pigment, size 0.5 μm, and a loading of 0.5 lbs/gal(59.91 g/L) has the following characteristics Good hiding power,excellent heat stability, jet black masstone, excellent UV stability andoutdoor weather resistance, excellent humidity resistance, excellentcorrosion resistance and hardness.

Example 50

A very high temperature coating having a silicon based resin and havingpolysilocarb ceramic pigment, size 0.1 μm, and a loading of 0.2 lbs/gal(11.83 g/L) has the following characteristics Good hiding power,excellent heat stability, jet black masstone, excellent UV stability andoutdoor weather resistance, excellent humidity resistance, excellentcorrosion resistance and hardness.

Example 51

The VHTCs of Examples 48-50 are essentially free of heavy metals, havingless than about 1 ppm Mn, Cr, or other heavy metals, having less thanabout 0.1 ppm Mn, Cr, or other heavy metals, having less than about 0.01ppm Mn, Cr, or other heavy metals, less than about 0.001 ppm heavymetals, and having less than 0.0001 ppm heavy metals, and still morepreferably being free from any detectable heavy metals, using standardand established testing methods know to the industry. The PDC pigmentsused in the formulations can have less than about 100 ppm heavy metals,less than about 10 ppm heavy metals, less than about 1 ppm heavy metalsand less than about 0.1 heavy metals.

Example 52

A high-solids acrylic enamel mill base having 25% solvent (butylacetate), 20%≦0.2 μm polysilocarb ceramic pigment, and 55% resin. Themill base is then added to an acrylic isocyanate base at a ratio of 1:3.The acrylic enamel is sprayed onto a metal substrate and exhibits thefollowing features Gloss 20 degrees 95%, Gloss 60 degrees 99%, ColorDevelopment L 25, a 0, b-0.5

Example 53

A polysilocarb ceramic pigment of Examples 1-31 is a colorant suitableand advantageous in multiple industrial, architectural, marine andautomotive systems. The pigment is low dusting and easily disperses intoacrylics, lacquers, alkyds, latex, polyurethane, phenolics, epoxies andwaterborne systems providing a durable, uniform coating and pleasantaesthetic in both matte and gloss finishes. The polysilocarb ceramicpigment has low oil absorption, which among other things, permitsformulations to move to higher solids loading with lower VOC content.The pigment is substantially free, and preferably entirely free fromheavy metals.

Example 54

An embodiment of the polysilocarb ceramic pigment of Examples 1-31 is acolorant suitable and advantageous in multiple industrial settings andis non-conductive, acid, alkali resistant, and thermally stable up to700° C., and 800° C. and 900° C. and 1000° C.

Example 55

An embodiment of the polysilocarb ceramic pigment of Examples 1-31, hasadded to the precursors a filler that provides conductivity to thepyrolized pigment, is a colorant suitable and advantageous in multipleindustrial settings and is conductive, acid, alkali resistant, andthermally stable up to the melting temperature of the conductive filler.

Example 56

The polysilocarb ceramic pigment of Examples 1-6, 8, and 10-16 added atsufficient levels to obtain the required coverage by the appliancemanufacturer and applied to the interior of a microwave oven. Theinterior polysilocarb pigment coating has good gloss, hiding and isnon-arching during microwave use.

Example 57

A polysilocarb ceramic pigment has added to the precursor formulationscarbon black. The pyrolized filled polysilocarb pigment has the superiorwettability and dispersion performance of the net polysilocarb pigments,while having the cheaper carbon black material. The carbon black filleris a cheaper extender for the polysilocarb material.

Example 57a

The pigments of Example 57 have 20% carbon black filler.

Example 57b

The pigments of Example 57 have 30% carbon black filler.

Example 57c

The pigments of Example 57 have 40% carbon black filler.

Example 57d

The pigments of Example 57 have 50% carbon black filler.

Example 57e

The pigments of Example 57 have 60% carbon black filler.

Example 58

A polysilocarb formulation is cured to into the volumetric shape of abead. The end cured polysilocarb derived beads are, for example, addedto paints, glues, plastics, and building materials, such as dry wall,sheet rock, gypsum board, MDF board, plywood, plastics andparticleboard. The end cured polysilocarb derived beads, as additives,can provide, among other things, binding (e.g., serve as a binder),water resistivity, fire resistance, fire retardation, fire protectionand strength; as well as, abrasion resistance, wear resistance,corrosion resistance and UV resistance, if located at or near thesurface of the shape.

Example 58a

In addition to a beads of Example 58, the polysilocarb additives can bein the form of a fine powder, fines, a power or other dispersible forms.The dispersible form can be obtained by grinding or crushing largercured structures. They also may be obtained through the curing processif done under conditions that cause the structure to fracture, crack orbreak during curing. These dispersible forms may also be obtained byother processing techniques, for example, spray curing or drying.

Example 59

A polysilocarb formulation is cured to into the volumetric shape of abead. The beads are then pyrolized to for a polysilocarb derived ceramicbead. The polysilocarb derived ceramic beads are added, for example, topaints, glues, plastics, and building materials, such as dry wall, sheetrock, gypsum board, MDF board, plywood, plastics and particleboard. Theceramic polysilocarb beads, as additives, can provide, among otherthings, fire resistance, fire retardation, fire protection and strength.

In addition to a bead the polysilocarb additives can be in the form of afine power, fines, a power or other dispersible forms. The dispersibleform can be obtained by grinding or crushing larger cured or pyrolizedstructures. They also may be obtained through the curing or pyrolysisprocess if done under conditions that cause the structure to fracture,crack or break during curing or pyrolysis.

Example 60

A polysilocarb formulation is pyrolized in the form of a volumetricstructure. The ceramic polysilocarb derived volumetric structureexhibits reflective and refractive optical properties, such asopalescence, shine, twinkle, and sparkle. These optical properties arepresent when the structure is black in color, (e.g., no colorant hasbeen added to the formulation); or if the structure is colored (e.g.,any color other than black, e.g., white, yellow, red, etc.).

Example 61

The volumetric structure of Example 60 is a work surface, such as atable top, a bench top, an insert, or a kitchen counter top, to name afew.

Example 62

The volumetric structure of Example 61 has other colorings or additiveto provide simulated granite like appearance.

Example 63

The volumetric structures of Example 60 are small beads that are blackand exhibit a twinkle, opalescence or shin. These beads are incorporatedinto a paint formulation. The patent formulation is for example appliedto automobiles or appliances. It provides a flat or matte finish, whichis for example popular on newer BMWs and Mercedes, but adds to thatmatte finish an inner sparkle or luster. Thus, the polysiloxane basedpaint formulation provides a sparkle matte finish to an automobile,appliance or other article.

Example 64

Pyrolized polysilocarb beads having a size of from about 100 to about1,000 microns are added to a paint formulation at a loading of fromabout 1% to about 40%.

Example 65

The paint of Example 64 in which the paint formulation, is an automotivepaint, and is colored blue and the beads are the same blue color as thepaint, and have size of 350 microns (+/−5%) and a loading of about 25%.

Example 66

The paint of Example 64 in which the beads are not colored, i.e., theyare black, and have a size ranging from about 300-500 microns, and thepaint is a black, although not necessarily the same black as the beads.

Example 67

A latex paint formulation having pyrolized polysilocarb power added intothe formulation, the power has a size range of about 0.5-100 microns,and the powder has a loading of about 15%.

Example 68

The paint formulation of Example 66 is an enamel.

Example 69

The polysilocarb ceramic pigments can be made from the pyrolysis of anypolysilocarb batches that are capable of being pyrolized. Thepolysilocarb pigment material can be provided, for example, as beads,powder, flakes, fines, or other forms that are capable of beingdispersed or suspended in the paint formulation (e.g., platelets,spheres, crescents, angular, blocky, irregular or amorphous shapes).Beads can have a size of from about 100 to about 1,000 microns indiameter. Powders can have a particle size range of from about 0.5 toabout 100 microns in diameter. Any subset range within these ranges cancreate the desired effect or color. Larger and smaller sizes may alsoprovide the desired effects in other formulations. For example: 300-500micron range beads; 350 (+/−5%) micron beads; 5-15 micron range powder.Particle size ranges for a particular polysilocarb ceramic pigmentpreferably range as tight as +/−10% and more preferably +/−5%. The rangemay also be broader in certain applications, e.g., 100-1000 for beads,and e.g., 0.5-100 for powders. The density and hardness of thepolysilocarb ceramic pigment can be varied, controlled and predeterminedby the precursor formulations used, as well as the curing and pyrolizingconditions. The polysilocarb ceramic pigments can provided enhancedcorrosion resistance, scratch resistance and color (UV) stability topaint formulations. Optical properties or effects of the polysilocarbceramic pigment can, among other ways, be controlled by the use ofdifferent gases and gas mixtures, as well as other curing and pyrolysisconditions. The polysilocarb ceramic pigment loading can be usedanywhere from a 1% to a 40% in order to achieve the desired effect.Further, the use of the polysilocarb ceramic pigments can provideenhanced flame retardant benefits. The polysilocarb ceramic pigmentshave a further advantage of being low dusting, and easily mixed into anytype of paint formulations, e.g., latex, enamel, polyurethanes,automotive OEM and refinish, alkyd, waterborne, acrylic and polyolcoatings formulations. The polysilocarb ceramic pigments can also beused as a fine colorant in inks and graphic arts formulations.

Example 70a

A ceramic ink comprising 10-30% polysilocarb black ceramic pigment,10-60% zinc or bismuth submicron glass frit, 10-20% Sucrose acetateisobutyrate, 4-15% hydrocarbon resin, 5-15% ethylene glycol.

Example 70b

A packaging ink comprising 2-30% polysilocarb black ceramic pigment,5-15% nitrocellulose resin, 25-35% ethanol solvent, 10-20% ethyl acetatesolvent, 1-2% citrate plasticizer, 1% polyethylene wax solution, 5-10%additives.

Example 71a

A plastic comprising of 75-80% Polypropylene copolymer, 1-6%polysilocarb black ceramic pigment, 15-20% talc

Example 71b

A plastic comprising of 94-98% HDPE plastic and 2-6% polysilocarb blackceramic pigment

Example 71c

A plastic comprising 94-98% polycarbonate and 2-6% polysilocarb blackceramic pigment

Example 71d

A plastic comprising 94-99% polyamide and 1-6% polysilocarb blackpigment

Example 71e

A rubber comprising of 55-65% EPDM elastomer, 10-40% polysilocarb blackceramic pigment, 5-10% paraffinic extender oil, 3% zinc oxide, 0.5%stearic acid, 0.9% sulfur, 0.9% tetramethyl thiuram monosulphide, 0.5%antioxidant, 0.3% mercaptobenzothiazole.

Example 71f

A rubber based on 60-70% Fluoroelastomer, 10-20% polysilocarb blackceramic pigment, 1-2% dimethyl-di (t-butyl peroxy)hexane, 1-1.5%triallyl iscocyanurate, 1-1.5% Zinc oxide.

Example 71g

A plastic comprising 75-80% ABS plastic, 2-6% polysilocarb black ceramicpigment, 15-20% talc.

Example 71h

A phenolic molding compound comprising 50% phenolic resin, 35-45% talc,5-15% polysilocarb black ceramic pigment.

Example 71i

A Thermoplastic olefin compound comprising 60% polypropylene copolymer,10-15% polyolefin elastomer, 2-6% polysilocarb black ceramic pigment,10% talc, 0.2% antioxidant.

Example 71j

A siloxane compound comprising 75-95% siloxane, 1-18% fumed silica, and1-5% polysilocarb black ceramic pigment.

Example 71k

A siloxane compound comprising 50-80% siloxane, 1-20% fumed silica,1-20% talc or other white filler, and 0.5-5% polysilocarb black pigment.

Example 72

A lawnmower piston assembly made from A phenolic molding compoundcomprising 50% phenolic resin, 35-45% talc, 5-15% polysilocarb blackceramic pigment.

Example 73

A car dashboard made from a plastic comprising of 75-80% Polypropylenecopolymer, 1-6% polysilocarb black ceramic pigment, 15-20% talc.

Example 74

A car bumper made from a thermoplastic olefin compound having 60%polypropylene copolymer, 10-15% polyolefin elastomer, 2-6% polysilocarbblack ceramic pigment, 10% talc, 0.2% antioxidant

Example 75

A high temperature stable pump housing coating having 30-35% siliconeresin, 8-30% micronized mica filler, 1-15% polysilocarb black ceramicpigment, 35-50% xylene solvent.

Example 76

An adhesive comprising 7-10% chlorinated rubber, 5-7% polysilocarbceramic black pigment, 4-5% phenol formaldehyde resin, 1-2% fumedsilica, 1-2% zinc oxide, 50-6-% methyl ethyl ketone solvent, 5-10%xylene solvent.

The primary focus of the specification is on black pigment andadditives. It should be understood, however, that other colors ofpolymer derived ceramic pigments and preferably polysilocarb derivedceramic pigments can be utilized. These embodiments can have colorants,or fillers that impart different colors to the ceramic pigment. Suchcolorants can be for example glazes or other fillers or additives thatmaintain their color properties under pyrolysis conditions.

It is noted that there is no requirement to provide or address thetheory underlying the novel and groundbreaking processes, materials,performance or other beneficial features and properties that are thesubject of, or associated with, embodiments of the present inventions.Nevertheless, various theories are provided in this specification tofurther advance the art in this area. These theories put forth in thisspecification, and unless expressly stated otherwise, in no way limit,restrict or narrow the scope of protection to be afforded the claimedinventions. These theories many not be required or practiced to utilizethe present inventions. It is further understood that the presentinventions may lead to new, and heretofore unknown theories to explainthe function-features of embodiments of the methods, articles,materials, devices and system of the present inventions; and such laterdeveloped theories shall not limit the scope of protection afforded thepresent inventions.

The various embodiments of formulations, batches, materials,compositions, devices, systems, apparatus, operations activities andmethods set forth in this specification may be used in the variousfields where pigments and additives find applicability, as well as, inother fields, where pigments, additives and both, have been unable toperform in a viable manner (either cost, performance or both).Additionally, these various embodiments set forth in this specificationmay be used with each other in different and various combinations. Thus,for example, the configurations provided in the various embodiments ofthis specification may be used with each other; and the scope ofprotection afforded the present inventions should not be limited to aparticular embodiment, configuration or arrangement that is set forth ina particular embodiment, example, or in an embodiment in a particularFigure.

The invention may be embodied in other forms than those specificallydisclosed herein without departing from its spirit or essentialcharacteristics. The described embodiments are to be considered in allrespects only as illustrative and not restrictive.

1. A coating formulation comprising: a first material and a secondmaterial; wherein the first material defines a first material weightpercent of the coating formulation and the second material defines asecond material weight percent of the coating formulation; wherein thesecond material is a black polymer derived ceramic material comprisingsilicon, oxygen and carbon having from about 30 weight % to about 60weight % silicon, from about 5 weight % to about 40 weight % oxygen, andcarbon; wherein about 20 weight % to about 80 weight % of the carbon isfree carbon; and wherein the first material weight percent is largerthan the second material weight percent. 2-20. (canceled)
 21. Thecoating formulation of claim 1, wherein the first material comprises asystem selected from the group of systems consisting of acrylics,lacquers, alkyds, latex, polyurethane, phenolics, epoxies andwaterborne.
 22. The coating formulation of claim 1, wherein the firstmaterial comprises a material selected from the group consisting ofHDPE, LDPE, PP, Acrylic, Epoxy, Linseed Oil, PU, PUR, EPDM, SBR, PVC,water based acrylic emulsions, ABS, SAN, SEBS, SBS, PVDF, PVDC, PMMA,PES, PET, NBR, PTFE, siloxanes, polyisoprene and natural rubbers. 23.The coating formulation of claim 1, wherein the coating formulation is apaint formulation selected from the group consisting of oil, acrylic,latex, enamel, varnish, water reducible, alkyd, epoxy, polyester-epoxy,acrylic-epoxy, polyamide-epoxy, urethane-modified alkyd, andacrylic-urethane.
 24. The coating formulation of claim 1, wherein thecoating comprises a coating selected from the group consisting ofindustrial coatings, residential coatings, furnace coatings, enginecomponent coatings, pipe coatings, and oil field coatings. 25-33.(canceled)
 34. A coating formulation comprising: a carrier material anda black polymer derived ceramic pigment comprising silicon, carbon andoxygen having from about 30 weight % to about 60 weight % silicon, fromabout 5 weight % to about 40 weight % oxygen, and at least 5 weight %carbon, and wherein about 20 weight % to about 80 weight % of the carbonis silicon-bound-carbon.
 35. (canceled)
 36. A coating comprising: afirst material and a second material; wherein the first material definesa first material weight percent of the coating formulation and thesecond material comprises a second material weight percent of the totalcoating formulation; and wherein the second material is a black polymerderived ceramic material comprising silicon, oxygen and carbon havingfrom about 15.3 mole % to about 63.1 mole % silicon, from about 8.8 mole% to about 56.8 mole % oxygen, and at least about 6.3 mole % carbon, andwherein about 20 weight % to about 80 weight % of the carbon issilicon-bound-carbon, and the first material weight percent is largerthan the second material weight percent. 37-59. (canceled)
 60. A blackpolysilocarb derived ceramic pigment comprising silicon, oxygen andcarbon, having from about 15.3 mole % to about 63.1 mole % silicon, fromabout 8.8 mole % to about 56.8 mole % oxygen, and at least about 6.3mole % carbon, and wherein about 20 weight % to about 80 weight % of thecarbon is silicon-bound-carbon and about 80 weight % to about 20 weight% of the carbon is free carbon.
 61. The black polysilocarb derivedceramic pigment of claim 60, wherein the pigment defines a blacknessselected from the group consisting of: PMS 433, Black 3, Black 3, Black4, Black 5, Black 6, Black 7, Black 2 2×, Black 3 2×, Black 4 2×, Black5 2×, Black 6 2×, and Black 7 2×.
 62. The black polysilocarb derivedceramic pigment of claim 60, wherein the pigment defines a blacknessselected from the group consisting of: Tri-stimulus Colorimeter of Xfrom about 0.05 to about 3.0, Y from about 0.05 to about 3.0, and Z fromabout 0.05 to about 3.0; a CIE L a b of L of less than about 40; a CIE La b of L of less about 20; a CIE L a b of L of less than 50, b of lessthan 1.0 and a of less than 2; and a jetness value of at least about 200M_(y).
 63. The black polysilocarb derived ceramic pigment of claim 60,wherein the pigment is a UV absorber.
 64. The black polysilocarb derivedceramic pigment of claim 60, wherein the pigment has an absorptioncoefficient of greater than 500 dB/cm/(g/100 g).
 65. The blackpolysilocarb derived ceramic pigment of claim 62, wherein the pigmenthas an absorption coefficient of greater than 500 dB/cm/(g/100 g). 66.The black polysilocarb derived ceramic pigment of claim 60, wherein thepigment has an absorption coefficient of greater than 1,000 dB/cm/(g/100g).
 67. The black polysilocarb derived ceramic pigment of claim 60,wherein the pigment has an absorption coefficient of greater than 5,000dB/cm/(g/100 g).
 68. The black polysilocarb derived ceramic pigment ofclaim 60, wherein the pigment has an absorption coefficient of greaterthan 10,000 dB/cm/(g/100 g).
 69. The black polysilocarb derived ceramicpigment of claim 60, wherein the pigment comprises an agglomerate ofprimary pigment particles.
 70. The black polysilocarb derived ceramicpigment of claim 69, wherein the agglomerate has a size D₅₀ of at leastabout 10 μm.
 71. The black polysilocarb derived ceramic pigment of claim70, wherein the primary pigment particles have a size D₅₀ of less thanabout 1 μm.
 72. The black polysilocarb derived ceramic pigment of claim70, wherein the primary pigment particles have a size D₅₀ of less thanabout 1 μm.
 73. The black polysilocarb derived ceramic pigment of claim70, wherein the agglomerate has a strength A_(s) and the primaryparticle has a strength PP_(s) and PP_(s) is at least 100 times greaterthan A_(s).
 74. The black polysilocarb derived ceramic pigment of claim70, wherein the agglomerate has a strength A_(s) and the primaryparticle has a strength PP_(s) and PP_(s) is at least 500 times greaterthan A_(s).
 75. The black polysilocarb derived ceramic pigment of claim70, wherein the agglomerate has a strength A_(s) and the primaryparticle has a strength PP_(s) and PP_(s) is at least 1,000 timesgreater than A_(s).
 76. The black polysilocarb derived ceramic pigmentof claim 60, wherein the pigment has an oil absorption of less thanabout 50 g/100 g.
 77. The black polysilocarb derived ceramic pigment ofclaim 65, wherein the pigment has an oil absorption of less than about50 g/100 g.
 78. The black polysilocarb derived ceramic pigment of claim69, wherein the pigment has an oil absorption of less than about 50g/100 g.
 79. The black polysilocarb derived ceramic pigment of claim 60,wherein the pigment has an oil absorption of less than about 20 g/100 g.80. The black polysilocarb derived ceramic pigment of claim 65, whereinthe pigment has an oil absorption of less than about 20 g/100 g.
 81. Theblack polysilocarb derived ceramic pigment of claim 69, wherein thepigment has an oil absorption of less than about 20 g/100 g.
 82. Theblack polysilocarb derived ceramic pigment of claim 60, wherein thepolymer derived ceramic pigment has a primary particle D₅₀ size of fromabout 0.1 μm to about 1.5 μm.
 83. The black polysilocarb derived ceramicpigment of claim 60, wherein the polymer derived ceramic pigment has aprimary particle D₅₀ size of greater than about 0.1 μm.
 84. The blackpolysilocarb derived ceramic pigment of claim 60, wherein the polymerderived ceramic pigment has a primary particle D₅₀ size of less thanabout 10.0 μm.
 85. The black polysilocarb derived ceramic pigment ofclaim 60, wherein the polymer derived ceramic pigment has a primaryparticle D₅₀ size of from about 0.1 μm to about 3.0 μm.
 86. The blackpolysilocarb derived ceramic pigment of claim 60, wherein the polymerderived ceramic pigment has a primary particle D₅₀ size of from about 1μm to about 5.0 μm.
 87. The black polysilocarb derived ceramic pigmentof claim 60, wherein the pigment is microwave safe.
 88. The blackpolysilocarb derived ceramic pigment of claim 65, wherein the pigment ismicrowave safe.
 89. The black polysilocarb derived ceramic pigment ofclaim 66, wherein the pigment is microwave safe.
 90. The blackpolysilocarb derived ceramic pigment of claim 69, wherein the pigment ismicrowave safe.
 91. The black polysilocarb derived ceramic pigment ofclaim 75, wherein the pigment is microwave safe.
 92. The blackpolysilocarb derived ceramic pigment of claim 60, wherein the pigment isnon-conductive.
 93. The black polysilocarb derived ceramic pigment ofclaim 60, wherein the pigment is hydrophilic.
 94. The black polysilocarbderived ceramic pigment of claim 60, wherein the pigment is hydrophobic.